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BACKGROUND OF THE INVENTION
The present invention relates to a positive displacement internal combustion engine with multiple stages of compression and expansion reaching very high pressures and having density control of engine torque.
It is known that increasing the expansion ratio of a reciprocating internal combustion engine extracts more energy during the expansion of the combustion gases. Therefore, the thermodynamic efficiency increases as the expansion ratio increases. For constant volume combustion, the theoretical thermal efficiency equals:
1-1/r.sup.(k- 1) (1)
where r is the expansion ratio and k is the adiabatic expansion coefficient, which for air at room temperature is 1.4.
Conventional Otto cycle engines usually have the same compression and expansion ratios, which are selected so that the fuel/air mixture is compressed to a point below which spark ignition does not cause detonation. Detonation depends on the anti-knock characteristics of the fuel and on the combustion chamber design. The ratio is usually about 7 in automobile engines using regular fuel, but the ratio can be over 10 in aircraft engines. Diesel engines also have equal compression and expansion ratios, but the air is compressed to a point where the injection of fuel causes ignition.
Multiple staging has been known as a way of using more of the available energy left after expansion in an earlier stage. Early multi-staging is taught in conjunction with steam engines. Drautz, U.S. Pat. No. 423,224 (1890) is an example of a multi-stage steam engine. The last stage may expand steam to sub-atmospheric pressure. Turbo machinery has also used multi-staging. In reciprocating aircraft engines, the supercharger is driven by elevated pressure exhaust gas at high temperature to drive a compressor to compensate for decreased air density at high altitude Multi-staging has also been proposed for positive displacement rotary engines such as that disclosed in Hubers, U.S. Pat. No. 3,783,615 (1974). Multiple staging was important in rotary engines so that the engines could reach conventional compression ratios because positive displacement mechanisms in rotary engines have low efficiencies except at low pressure ratios.
Thermodynamic advantages of multi-staging are understood, but the problems in achieving these advantages in a practical manner have prevented their implementation. Theoretical problems such as detonation, increased heat transfer losses, large mechanical forces, increased friction losses, transfer losses, large size, complexity and many other smaller problems have contributed to the lack of interest in developing such an engine. Moreover, many of the tradeoffs in basic engine design took place when the fuel was very inexpensive and there was less demand for increased engine efficiency.
Pollution, heat dissipation and low efficiency for power variation are among the potential problems confronting present engineers. Engine efficiency also suffers from heat dissipation, which can increase as compression and expansion ratios increase. The heat loss represents energy not available for useful work. Conventional engines have no means to minimize the loss of available work with heat loss. Heat loss not only results in theoretical loss of available energy, but the engine must also drive equipment to cool heated engine parts.
Throttling the charge (the amount) of fuel/air mixture flowing to the combustion chamber at any time is the conventional way of varying engine torque and power. Throttling results in large efficiency losses, which are caused by fluid flow losses and pumping. To compensate for these losses, vehicles use transmissions of up to five speeds for automobiles and up to twenty speeds for large trucks.
Another problem with conventional engines occurs because of incomplete mixture of fuel and air injected into the combustion chamber. If the fuel and air were mixed uniformly a leaner mixture could be used.
SUMMARY OF THE INVENTION
One of the principal objects of the present invention is to disclose and provide an internal combustion engine that is substantially more efficient than present engines. The theoretical efficiency in standard engines is roughly estimated by the equation:
1-1/r.sup.(0.3) ( 2)
Raising the expansion ratio, r, increases efficiency. The compression ratio is also increased. The present invention uses compresion ratios as high as 40 to 1 or higher. When the fuel/air mixture is compressed that much, the increase in temperature would normally cause detonation during burning. The present invention avoids the detonation that would take place at the higher compression ratios because compression which takes place in two or more stages with cooling before the last stage of compression lowers the final compression temperature below that of a conventional engine.
The higher density of the working fluid reduces the combustion chamber dimensions, which in turn reduces the time of ignition and burning. The tendency to detonate is also reduced as the time of ignition and burning is reduced.
The next principal object of the present invention is to provide a more efficient means of varying the output torque over a wide range of values. Present standard engines vary torque with multiple gear transmissions. Achieving this objective in cars or trucks could reduce transmission size and decrease the number of gear changes. Controlling the fuel/air ratio and throttle controls provide variation in current engines, but efficiency drops off rapidly at low torque.
The multi-staged engine of the present invention provides an additional means, which is more efficient, for controlling the density of the working fluid. The controlled in the present invention limits the admission of working fluid to the compressor or limits the flow from the compressor to the accumulator. These methods drop the compression ratio so there is some loss in efficiency for thermodynamic reasons, but there is not an increase in pumping losses that occur with standard throttling. Losses from fluid flow, friction and heat transfer do not drop as fast as the drop in density.
The next primary object of the present invention is to disclose and provide an internal combustion engine of reduced size and weight. Each piston in a standard, four cylinder, four cycle engine has a power stroke every 720°. In the multi-staged engine of the present invention, a post-expansion piston has a power stroke every 360°, twice as often as the four cycle combustion stroke. Thus, the post-expansion stage can take the place of two combustion cylinders. Therefore, the multi-staged engine of the present invention with two combustion cylinders and a single post-expansion cylinder can provide approximately the same power uniformity as a four cylinder standard engine.
Locating the post-expansion chamber between and in line with two combustion chambers and having the two combustion pistons 180° out of phase with the larger and heavier post-expansion piston, makes a balanceable engine arrangement.
A further object of the present invention is to provide an engine that can use two sides of single piston for the different tasks, one side for pre-compression of the working fluid before combustion and the other side for post-expansion of the working fluid. The use of such a dual piston eliminates one set of large piston rings and reduces the overall size of the engine.
If the pre-compression cylinder is to have the same working fluid volume intake as standard engine cylinders, the pre-compression piston must have twice the area of the piston of a standard four cylinder engine. The greater efficiency of the present invention reduces the required fuel/air mixture intake, but a lower fuel/air ratio (for less pollution) increases the required air intake. With other factors, the area of the pre-compression and post-expansion pistons could be about 21/4 times the area of standard, comparable engine pistons. The small combustion cylinders in the present invention are about one-third the diameter of the post-expansion and pre-compression pistons.
The next principal object of the present invention is to provide an internal combustion engine with reduced pollution. It is known that higher engine temperatures increase the concentration of pollutants in the working fluid. The engine of the present invention can operate at lower fuel/air ratios, which in turn reduces the temperature and pollution. The lower compression ratio in the combustion chambers of the present invention reduces the temperature further. That occurs because the fuel/air mixture is ignited from a lower starting temperature. Flame travel velocity decreases at lower fuel/air ratios. The present invention uses small combustion chambers to compensate for decreased velocity of flame travel through decreased distance of flame travel.
The present invention also uses an accumulator after pre-compression but before cooling. The accumulator provides complete vaporization of the fuel, which improves its combustion characteristics. Also, a more efficient engine uses less fuel, which proportionally results in less pollution.
The next principal object of the present invention is to disclose and provide a spark ignition engine that can use a wider range of fuels. Because the engine cools the fuel/air mixture before the final stage of compression and because of its lower combustion stage compression ratio, it operates at reduced temperatures. The engine does not require higher octane fuel that previous high-compression engines require. Spark ignition airplane engines would not require special fuels.
A further expansion of the working medium takes place in a post-expansion cylinder. The expanding working medium acts on a post-expansion piston in the post-expansion cylinder, which drives the crankshaft 180° of crankshaft phase later than the pistons of the combustion chambers. This arrangement allows the multi-staged engine with two combustion chambers to have power output of similar uniformity to a conventional four cylinder engine. By proper coordination of the valves between the combustion and post-expansion chambers, there can be an increase in efficiency for reasons explained in more detail below. The design of the piston face, which can occupy portions of the passages between the chambers, can affect the flow of gases, but is designed to reduce the post-expansion dead volumes.
The present invention takes advantage of pre-compression so that the actual compression that takes place in the combustion chambers can be minimized. The device can use smaller pistons. Moreover, the present invention can use as few as two combustion chambers. The reduced size and number of the combustion chambers reduces the heat transfer area and ultimate heat transfer to the surroundings.
Heat loss represents energy that is not available for work. It is recognized that because of additional heat losses, raising the compression ratio above customary amounts in conventional engines can result in decreased output. A decrease in heat transfer results in a more efficient engine. The lower compression ratios that take place in the combustion chamber and a lower fuel to air ratio gives lower combustion temperatures. This decrease permits higher combustion chamber surface temperatures.
The present invention can use one direction of the stroke of the piston to compress the working fluid and to receive and expand combustion products on the other side of the piston. By using the same piston to perform two different functions, engine size can be greatly reduced. The various other components that function with the piston such as crankshaft eccentrics, bearings, piston rods and rings can be reduced also.
The pre-compression piston could first compress and then discharge the fuel/air mixture through a valve normally during the approximately the last 50° of crank rotation. The engine combustion chamber takes in the working fluid during approximately 180° of crank rotation. Pressure variations in the combustion chamber which would be caused by this lack of matching, can be reduced by discharging the working fluid from the pre-compressor in a gas reservoir of substantial volume, the accumulator in the present invention. A larger reservoir decreases the pressure fluctuations. The volume of the reservoir also includes the volume of all ducts between the pre-compressor discharge valve and the combustion chamber intake valves and the high pressure passages, collectors and headers of the heat exchanger that is between the valves. Dynamic acumulators and compressors that have a gas delivery but more closely match the intake requirements of the combustion chambers (e.g. Lysholm compressors, multiple piston compressors) will greatly reduce the required reservoir volume.
Another factor affecting accumulator size will be the design of the engine accessories. A tank accumulator could be reduced in size substantially, and could even be eliminated if the ducts and heat exchanger collectors and heaters are oversized. If the reservoir volume is very large, the response to the accelerator push rod is slow because time is required to build up or drop off pressure. This slow response makes starting take less energy for cranking. If faster response is desired a dynamic accumulator or a smaller reservoir volume can be used. This would require larger starters and batteries. Although the present invention uses a tank as an accumulator, the accumulator of the present invention need not be an added object. Any means for providing high pressure gas holding capacity sufficient to reduce pressure variations from the pre-compressor as a result of combustion chamber intake to decrease fluid flow losses would perform the function of an accumulator.
The present invention includes a crankshaft or other comparable piston driver. The crankshaft drives an intake or pre-compression piston in an intake or pre-compression cylinder. During the piston movement of the piston away from its cylinder head, the fuel/air mixture is drawn into the pre-compression cylinder. During movement of the piston toward the head, the piston compresses the fuel/air mixture. The compressed fuel/air mixture passes into an accumulator. The accumulator temporarily holds the fuel/air mixture at an elevated pressure and allows the fuel and air to mix completely. A reed valve or other valve that opens under pressure to allow flow in the direction of the pressure may connect the pre-compression chamber with the accumulator so that the compressed fuel/air mixture only flows into the accumulator when the pressure in the pre-compression chamber exceeds the pressure in the accumulator.
The fuel/air mixture next passes through a heat exchanger to cool it before it is taken into one of two combustion chambers, which are 360° out of phase with each other. The expanding combustion products in the combustion chambers exert force on the pistons to drive the crankshaft. The combustion products from the combustion chamber continue expanding as they flow into a post-expansion chamber or cylinder were they drive a post-expansion piston that is also connected to the crankshaft. Added efficiency is obtained because the work that can be obtained from further expanding of the combustion products drives the post-expansion piston, that is larger than the pistons in the combustion chambers. This piston is 180° out of phase with both smaller pistons in the combustion chambers.
In one embodiment, the functions of the pre-compression and post-expansion pistons are combined into a single piston in one chamber. One side of the chamber is used for pre-compression and the other side of the chamber is used for post-expansion. This arrangement allows for a compact in-line design in which the single, large pre-compression/post-expansion chamber is between the two smaller combustion chambers. Many other features and advantages of the present invention are described in the "Detailed Description of the Preferred Embodiment" and in the drawings.
The exemplary embodiment illustrates one set of requirements only. Aircraft, automobile, truck, boat and other engines each have differing requirements that may require substantial modification to the components of the engine of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a log-log graph of the relationship of the density and the temperature of the working fluid in the exemplary embodiment of the multi-stage engine of the present invention.
FIG. 2 is a log-log graph of the relationship of the density and pressure of the working fluid in the exemplary embodiment of the multi-stage engine of the present invention.
FIG. 3 is an idealized representation of the multi-staged internal combustion engine of the present invention with one pre-compression stage.
FIG. 4 is a cut-away view of another specific embodiment of the multi-staged internal combustion engine of the present invention.
FIG. 5 is a partial end view of FIG. 4 showing some of the components of the multi-staged engine of the present invention. Some of the cams that drive the valve are shown in detail.
FIG. 6 is another idealized representation of the engine of the present invention. It has two pre-compression stages rather than the single stage that the FIG. 3 engine has.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Adiabatic expansion and compression are straight lines on log-log coordinates. In FIG. 1, which represents the relationship of temperature to density of one configuration of the present combustion engine, the slopes are k-1, where k is the specific heat at constant pressure divided by the specific heat at constant volume for the working medium. See equation 1. In FIG. 2, which is the pressure versus density graph, the slopes of adiabatic expansion and compression are k. Both figures assume that cooling takes place at constant pressure and that combustion takes place at constant volume.
In FIG. 1, the fuel/air mixture intakes at point a, 0.0765 lbs/ft 3 and 530° R (standard ambient conditions). The working fluid is then pre-compressed to a 0.306 lbs/ft 3 density at 920° R to point b. The slope between points a and b is approximately 0.4, which equals k-1. The working fluid is then cooled in a heat exchanger at constant pressure to point c at a density of 0.53 lbs/ft 3 at 540° R. The slope of line b-c=-1. As explained in more detail with reference to an actual engine, the working fluid is then mixed with residual engine gas, which is at a temperature of approximately 1700° R. The mixing reduces the density of the working fluid to approximately 0.43 lbs./ft. 3 at 650° R to point d back along the same slope line.
The working fluid then undergoes engine compression to a density of 1.68 lbs/ft 3 at 1100° R to point e. The working fluid does undergo some engine heating from point d to point e. The slope of that segment is 0.39. Combustion takes place at constant volume and density, which raises the temperature of the working fluid to 4,000° R to point f. The working fluid then undergoes engine expansion to a 0.43 lbs/ft 3 density at 2,500° R to point g. The slope of segment f-g is 0.25. The working fluid then transfers to the post-expansion chamber where the expansion continues to about 0.06 lbs/ft 3 density at 1125° R at point h. The slope of segment g-h is approximately 0.3. The spent working fluid is then exhausted to the atmosphere. Point i shows the condition of the residual gas, which mixes with and reheats the compressed working fluid that has been cooled in the heat exchanger.
In the pressure-density cycle of FIG. 2, the fuel/air mixture intakes at 0.0765 lbs/ft 3 density and 14.7 psi pressure, point j. The working fluid is then pre-compressed to 0.306 lbs/ft 3 density to 102 psi at point k. The slope of segment j-k equals 1.4. The heat exchanger cools the working fluid at constant pressure to 0.53 lbs/ft 3 . The working fluid is then mixed with residual engine gas which reduces the density to 0.43 lbs/ft 3 , still at constant pressure to point m.
The working fluid then undergoes engine compression to a density of 1.68 lbs/ft 3 at 700 psi to point n. The slope of segment m-n is 1.39. Combustion takes place at constant volume and density so that pressure rises by the same ratio that the absolute temperature rises to about 2,500 psi at point o. The working fluid then undergoes engine expansion to a density of 0.43 lbs/ft 3 at 400 psi to point p. The slope of segment o-p is 1.25. The working fluid then transfers to the post-expansion chamber where the expansion continues to above 0.06 lbs/ft 3 density at point q. The slope along segment p-q is 1.3. At point q, the spent working fluid is exhausted to the atmosphere. Point r shows the residual gas reheating the compressed working fluid from the heat exchanger.
In the exemplary embodiment, a considerable amount of residual gas mixes with the incoming fuel/air supply during intake into the combustion chambers. In the illustrated embodiment, the residual gas is 25% by volume and 10% by weight. As a result, the cycle above 102 psi (point m in FIG. 2) has a mass 10% greater than the working fluid below that pressure. The work of compression and the work given off during expansion are comparably affected. Actually, the thermodynamic cycles of FIGS. 1 and 2 are idealized because they show the residual gas being removed at 102 psi. This gas is actually expanded to a much lower pressure and then recompressed to this value as the dashed lines show.
The theoretical temperature of the fuel/air mixture just before combustion in the present invention is 1104° R. The final combustion temperature is 4000° R. In a conventional 7:1 compression ratio engine, the temperature is 1260° R just before combustion, and the combustion temperature is 5000° R. As is shown in the remaining figures, the diameter of the pistons in the combustion chambers is about half that of the diameter of the pistons in a conventional engine having the same power. The smaller chambers reduce the distance that the flame must travel, which in turn, reduces the time of ignition to about 35% of a conventional engine, especially if two spark plugs are used for each combustion chamber. This improvement in the factors causing ignition in the present invention more than compensates for the reduced speed of flame travel because of the lower fuel/air ratios and higher pressure. Detonation is prevented. Theoretically, the efficiency of the cycle is also improved by using leaner than stoichiometric fuel ratios because the leaner mixtures are closer to the thermodynamic air cycle. Essentially, making the mixture leaner increases the k value. A leaner mixture also results in lower combustion temperatures which also raises the k value. Therefore, it is desirable to be able to use leaner mixtures and to have combustion take place at lower temperatures.
FIG. 3 is an idealized representation of the internal combustion engine of the present invention. The exemplary embodiment in FIG. 3 (and FIG. 4) is a small engine for automotive use. For different conditions, the size, fuels and other requirements can be altered. As is conventional, crankshaft 1 rotates. The great majority of internal combustion engines use a crankshaft to convert reciprocating motion of pistons into rotary motion that an automobile, airplane or other device can use. Other systems exist for converting reciprocating linear motion to rotary motion. The Hermann can engine is an example. It should be recognized that the teachings of the present invention are adaptable to these other engines. Intake duct 14 receives fuel from injector 3 and air from air intake 2. Injector 3 is representative of a carburetor or fuel injector, which controls the fuel/air ratio. The quantity of fuel/air mixture is controlled by structure discussed below with reference to timing of the pre-compression inlet valve 15.
The fuel/air mixture passes into pre-compression chamber 18 when crankshaft 1 reciprocates piston rod 13 to pull pre-compression piston 11 away from head 12 (down in FIG. 3) in cylinder 10. Section 19 of crankshaft 1 rotates around the axis of the crankshaft between its top dead center position shown in FIG. 3, which corresponds to the closest movement of piston 11 toward head 12, and a bottom dead center position, which corresponds to the position of the piston farthest from head 12. Inlet valve 15 is open, and outlet valve 17 is closed as crankshaft section 19 pulls piston rod 13 to pull piston 11 downward.
As piston 11 moves down away from the head in pre-compression chamber 18 and valve 15 is open, a decrease in pressure in the chamber causes the fuel/air mixture to be drawn into the pre-compression chamber. Valve 15 may close when pre-compression piston 11 reaches its bottom dead center position, or the timing of its opening and closing may change in response to engine torque settings. Valve 17 remains closed.
Crankshaft section 19 continues to rotate from the bottom dead center position toward head 12 (up in FIG. 3) so that piston rod 13 pushes pre-compression piston 11 toward the head to compress the fuel/air mixture.
Outlet valve 17 opens when the pressure in pre-compression chamber 18 is equal to the pressure in accumulator 4. The compressed fuel/air mixture can flow past open valve 17 through duct 16 into accumulator 4. Accumulator 4 is a pressure tank in the exemplary embodiment, which functions to hold pressurized fuel/air mixture. In FIG. 3, the accumulator is shown to be above the engine, but it may be located in any convenient space. Ducting between outlet valve 17 and the combustion chambers as well as any other ducts and passages described below would function as an accumulator. A piston-type accumulator could also be used. Moreover, there are some type of pre-compressors that may not require large volumes of pressurized gas storage.
Through compression, the volume of fuel/air mixture in accumulator 4 is at an elevated temperature, which for the exemplary embodiment is approximately 460° F. (238° C.). The accumulator also retains the fuel/air mixture for a relatively long time. Therefore, all of the fuel should vaporize and mix thoroughly with the air.
Outlet valve 17 may be a reed valve (flexure-close off valve) that opens when the pressure in pre-compression chamber 18 exceeds the pressure within accumulator 4 during the movement of piston 11 toward head 12. The reed valve remains closed as long as the pressure in accumulator 4 exceeds the pressure in the pre-compression cylinder. When the engine is first started, the pressure within accumulator 4 is closer to atmospheric pressure. At that time, pressure in pre-compression cylinder 10 becomes greater than the pressure in the accumulator earlier during movement of piston 11 toward head 12. After some time, the pressure in accumulator 4 reaches a higher, steady state pressure. As explained in more detail below, the pressure in the accumulator can vary depending on required torque. The pressure in chamber 18 does not exceed the pressure in accumulator 4 until later in the upstroke (e.g., the last 50° of crank rotation). Reed valve 17 does not open until then. When the reed valve opens, however, the pressure differential is slight so that the velocity of the gas flow is low.
As explained in more detail below in conjunction with FIGS. 4 and 5, the timing of the opening and closing of inlet valve 15 may vary as a function of engine demand. At times of high power requirements, the engine requires large volumes of air and fuel. Valve 15 opens throughout movement of piston 11 away from head 12. When the engine is closer to idling speed, it is unnecessary to add large volumes of fuel/air mixture to accumulator 4. Valve 15 can open later during the movement of piston 11 away from head 12 and/or close earlier during the movement of the piston away from the head. Suggested structure for controlling valve 15 in response to power demands is addressed during the discussion of FIGS. 4 and 5.
Valve 17 is the reed valve, and valve 15 is the controlled valve in the exemplary embodiment. Valve 15 could be the reed valve, and valve 17 could be the controlled valve.
The fuel/air mixture next flows from accumulator 4 through duct 5 and through heat exchanger 6. High effectiveness heat exchanger 6 cools the fuel/air mixture, which then flows through ducts 24 and 34 into combustion chambers 28 and 38. The heat exchanger is one having a low pressure drop. Decreasing the temperature is desirable because the fuel/air mixture is further compressed in combustion chambers 28 and 38 as discussed below. By having the fuel/air mixture at a low initial temperature but at a high pressure, the fuel/air mixture can be compressed further and still remain below the point where detonation would take place during combustion.
Three or more stages of compression are also feasible, but the cost of providing the stages may outweigh the added efficiency that added stages provide. The FIG. 6 embodiment, described below, shows two pre-compression stages before the compression takes place in the combustion chambers.
Each of the two combustion chamber 28 and 38 of the present invention is generally conventional, but they are smaller than conventional chambers because they have higher inlet fuel/air mixture density. Pistons 21 and 31 reciprocate in cylinders 20 and 30 under the action of piston rods 23 and 33 driven by sections 29 and 39 of crankshaft 1. Both combustion chambers operate in a four cycle mode and repeat their operation every 720° of crankshaft rotation.
If the combustion chambers and pistons operated conventionally, section 29 of crankshaft 1 moves piston rod 23 and piston 21 away from head 22. Inlet valve 25 opens so that fuel/air mixture from accumulator 4 passing through heat exchanger 6 and duct 24 is drawn into combustion chamber 28. At approximately bottom dead center, inlet valve 25 closes. Outlet valve 27 remains closed. Piston 21 moves toward head 22 in its compression upstroke. When the fuel/air mixture is almost fully compressed, a spark plug (not shown) ignites the fuel/air mixture. The expanding combustion products would push piston 21 downward, away from the head to rotate section 29 of crankshaft 1.
The next stroke of piston 21 toward head 22 forces the exhaust gases past open valve 27 into duct 26. Valve 27 then would close and the four cycles would repeat. Duct 26 connects to the exhaust system. In the present invention, however, expanding combustion products that still can perform work, flow from duct 26 into post-expansion chamber 48, which is described in more detail below.
Combustion chamber 38 operates exactly the same as chamber 28, but the two pistons 21 and 31 are 360° out of phase with each other. That is, when fuel/air mixture burns and expands in chamber 28, piston 31 in chamber 38 moves away from head 32 and receives the fuel/air mixture past valve 35 through duct 34.
The combustion products from combustion chambers 28 and 38 flow through outlet ducts 26 and 36 and through inlet duct 44 into post-expansion chamber 48. Section 49 of crankshaft 1 acting through piston rod 43 reciprocates large post-expansion piston 41 in post-expansion cylinder 40. The post-expansion chamber receives exhaust gases from combustion chambers 28 and 38 during the movement of post-expansion piston 41 away from head 42 and the corresponding movement of piston 21 toward head 22 and then 360° of crankshaft rotation later from movement of piston 31 toward head 32. The ways in which the post-expansion chamber 48 and the combustion chambers 28 and 38 coordinate with each other and exchange the combustion products are important features of the present invention and are described in detail below.
Large, post-expansion piston 41 has a greater area than pre-compression piston 11 or than the combined areas of pistons 21 and 31 and is also greater in area. Large piston 41 moves 180° out of phase to smaller pistons 21 and 31. It is at top dead center when small pistons 21 and 31 are at bottom dead center. Note also that piston 41 completes its cycle during each 360° of crankshaft rotation, but smaller pistons 21 and 31 require 720° of crankshaft rotation to complete their cycles.
Valve 47, which is between post expansion chamber 48 and exhaust manifold 46, and valves 25, 27, 35 and 37 of combustion chambers 28 and 38 coordinate in one of two arrangements that vary from conventional internal combustion engines. In one procedure, valve 27 remains open during the expansion stroke of the gas in post-expansion chamber 48. Valve 47 opens slightly early as post-expansion piston 41 approaches bottom dead center. 360° of crank rotation later, valve 37 of combustion chamber 38 is open during the expansion stroke of gas in post-expansion chamber 48, and valve 47 also opens slightly early near the end of the downstroke of piston 41. Generally, only valves 25 and 27 and combustion chamber 28 are discussed in further detail.
By adjusting the timing of valves 27 and 47, it is possible for the pressure of the gas in chamber 28 to drop approximately to atmospheric pressure. Under those conditions, when valve 27 closes and then valve 25 opens and when piston 21 begins movement away from head 22, the amount of fuel/air mixture flowing from duct 24 into combustion chamber 28 exceeds the displacement that piston 21 normally produces. This occurs because the volume of residual exhaust gas from the previous cycle when piston 21 is at top dead center is much lower in pressure than the pressure in accumulator 4. The gas remaining in chamber 28 is compressed to equal the pressure of the fuel/air mixture in accumulator 4 by the in-rush of the fuel/air mixture as valve 25 opens. The ratio of the inlet gas volume while piston 21 is still at top dead center to the residual gas volume is approximately equal to the pre-compression ratio.
If valve 27 opens during the expansion stroke of piston 21, expanding gas flows through duct 44 into post-expansion chamber 48 where it continues to expand against post-expansion piston 41. The engine thus uses the work available in the expansion of combustion products. Valve 27 closes during movement of piston 41 toward head 42.
In the other method of operation, valve 27 closes before the exhaust stroke of piston 21 is completed. With proper timing, valve 27 closes when the gas in combustion chamber 28 will re-compress to the pressure of the gas in accumulator 4 at top dead center of piston 21. At the beginning of piston movement away from head 22, when valve 25 opens, there is no appreciable, rapid flow from duct 24 into combustion chamber 28 because the pressure in accumulator 4 and chamber 28 is almost equal. The work used to recompress the gas in combustion chamber 28 is returned to drive piston 21 during movement away from head 22.
The volume of fuel/air mixture that flows into combustion chamber 28 during movement of piston 21 away from head 22 is approximately equal to the displacement of piston 21. When section 29 of crankshaft 1 returns piston 21 to the top dead center position, the fuel/air mixture in combustion chamber 28 is compressed. At an appropriate time, a spark plug (not shown) generates a spark to ignite the fuel/air mixture. The temperature and pressure of the gas within combustion chamber 28 rises to approximately 4000° R and 2500 psi, and density remains constant.
The gas acts on the face of piston 21 to rotate crankshaft 1. Section f-g in FIG. 1 and section o-p in FIG. 2 show thermodynamically the expansion of the combustion products pushing piston 21 away from head 22. If the engine did not have post-expansion chamber 48 and piston 41, available work would be completed at 0.42 lbs/ft 3 (point g in FIG. 1 and point p in FIG. 2). The gas still has available work, which piston 4 uses.
Expanding combustion products in chamber 28 can be above atmospheric pressure if valve 47 closes before all of the gas in ducts 26, 36 and 44 and post-expansion chamber 48 reaches atmospheric pressure. The trapped gas is compressed so that the pressures in ducts 26, 36 and 44 and post-expansion chamber 48 equals the pressure in combustion chamber 28 at about top dead center of large piston 41. Thus, when valve 27 opens at about top dead center of large piston 41, there is no sudden flow of gas past valve 27, which would cause an energy loss. When valve 27 opens, duct 44 provides a direct connection between chambers 28 and 48. Now when small piston 21 moves toward head 22 and large piston 41 moves away from head 42, the total volume in two chambers 28 and 48 above the two pistons 21 and 41 increases. Somewhat before piston 21 reaches its top dead center position, valve 27 closes. As large piston 41 continues its movement toward bottom dead center, the total volume in ducts 26, 36 and 44 and chamber 48 continues to increase.
Valve 47 starts to open and is fully open shortly after piston 41 reaches the bottom dead center position. When valve 47 is open, piston 41 can expel gases to atmospheric pressure through duct 46. During the movement of piston 41 away from head 42, the pressure acting on its face produces work 180° later than that produced by regular pistons 21 and 31. Energy is supplied to crankshaft 1 by the two combustion pistons 21 and 31 and by post-expansion piston 41. As large piston 41 returns to the top dead center position, gas in chamber 48 flows out past valve 47 through exhaust manifold 46. The exhaust manifold may connect to an ejector (not shown).
The principal discussion has been with regard to the cooperation between small piston 21 and large piston 41. Piston 31 operates similarly to piston 21 except that its steps take place 360° later.
The main advantage of this design and method is that it eliminates the highly turbulent gas flow past the valves, which eliminates a very high heat transfer coefficient and pressure loss. The arrangement described has many other advantages. The present invention uses a heat exchanger 6 to cool the compressed fuel/air mixture. This arrangement permits overall compression ratios of over 30 without engine detonation and increases the pressure ratio of combustion to increase the availability of the energy released by combustion. As explained in conjunction with the FIG. 6 embodiment, it is also possible to control the temperature output of the heat exchanger to set the combustion chamber compression temperature. One can cool the engine with ambient air through the use of an ejector powered by exhaust gas from the engine.
The use of an accumulator 4 provides sufficient time for the fuel to vaporize completely and mix with the air. The volume of the accumulator is large enough that there is little reduction in pressure in accumulator 4 during the intake into combustion chambers 28 and 38. Becuase the large piston 41 is moving away from the head 42 when smaller, conventional pistons 21 and 31 are moving toward heads 22 and 32, the secondary expansion of the combustion products takes place in large chamber 48 180° of crankshaft travel after partial expansion takes place in the conventional combustion chambers 28 and 38. The present engine therefore provides power uniformities similar to that occurring in a conventional four-cylinder engine even though it has only two combustion chambers. The engine is relatively simple and much more efficient than a conventional engine.
Except when valves 27 and 37 are closed, valve actuation forces can remain at conventional levels if the pressure on both sides of the valves is balanced. Closing either combustion chamber valve 27 or 37 and of valve 47 of post-expansion chamber 48 can re-compress dead volume gas to the level of the pressure on the other side of the valve. Keeping equal pressure on both sides of the valves prevents sudden in-rushes of gases when the valves open and lowers the noise level of the engine. Each actual valve 27 and 37 needs to be pressure balanced because the pressure in ducts 26 or 36 can exceed the pressure in combustion chambers 28 or 38 during part of the cycle otherwise very stiff valve springs would be required. The pressure could inadvertently open the values if they were not balanced. The design of the pressure balanced valves is discussed with reference to the FIG. 4 embodiment.
FIGS. 4 and 5 show a less idealized representation of the internal combustion engine of the present invention than FIG. 3 shows. Crankshaft 101 (FIG. 4) rotates in bearing 181 in housing 180. An intake manifold receives fuel from an injector and air from an air intake (not shown in FIGS. 4 and 5).
In the idealized representation of FIG. 3, pre-compression cylinder 10 and post-expansion cylinder 40 were at opposite sides of the engine to permit explanation in the order that gas flowed through the engine. In the exemplary embodiment of FIG. 4, the pre-compression cylinder and the post-expansion cylinder are coaxial and form a dual cylinder. A single piston having two sides replaces the separate pre-compression and post-expansion pistons of FIG. 3.
In the exemplary embodiment of FIG. 4, dual piston 151 is mounted within dual cylinder 150. Piston rod 153 extends from crankshaft section 159 to the bottom, center of dual piston 151. Rings 183 around the outside of piston 151 prevents gas flow between the piston and the cylinder as the piston reciprocates. Top face 185 of piston 151 has a central conical indentation 187, downwardly sloping wall 169 and upwardly projecting duct filler 171. The top surface conforms generally to the shape of head 152 and valve disk 189 above piston 151. At top dead center of piston 151, duct filler section 171 extends into and occupies space 126 in a manner discussed below. The projection of duct 171 is element 171' and is shown in phantom.
The top portion of piston 151 in the upper part of dual cylinder 150 is the post-expansion element of the FIG. 4 embodiment. The pre-compression elements are on the bottom of the piston. Piston 151 has a flat, annular bottom wall face 191 extending between the space between outer wall 193 and inner surface 195 of piston 151. Wall 197 is concentric with wall 193, and bridge 199 connects the two inner walls 195 and 197 to create a space 201. The inside face of inner wall 197 has conventional elements (not shown) for attaching piston 151 to piston rod 153.
Annular bottom surface 192 extends inward from portion 194 of cylindrical wall 150 to inner cylindrical cup 196. Cup 196 extends into space 201 between walls 195 and 197. Cylinder wall 150 attaches to a part of cylinder wall 120 of combustion chamber 128. The operation of the combustion chambers are discussed below. Cooling fins 182 extend between walls 150 and 120. The engine provides cooling air to the fins in a manner discussed below.
Bottom wall 192 also includes a bearing extension 184 that also connects to housing 180. Bearing extension 184 holds a bearing 186 to support crankshaft 101. Rings 203 extend outward near the bottom of inner cylindrical wall 196 to contact cup 196 to seal off that portion of piston 151. The exemplary embodiment also has an additional outer oil ring 205.
In theory, it would be possible to mount rings 203 on the inner surface of wall 195 or on the outer surface of cup 196. There are, however, some difficulties. Therefore, the additional structure shown in FIG. 3 to mount the rings is desirable.
The fuel/air mixture enters the space between annular wall 191 of piston 151 and annular wall 192 of cylinder 150 through valves which are shown in FIG. 5 but are not shown in FIG. 4. The fuel/air mixture is drawn into the bottom portion of cylinder 150 during the movement of piston 151 toward head 152. This movement of piston 151 toward head 152 corresponds to the movement of piston 11 (FIG. 3) away from head 12 in pre-compression cylinder 10. The valves for accomplishing the admittance of the fuel/air mixture are discussed next.
The accelerator control attaches through appropriate structure to accelerator rod 207 (FIG. 5). When the accelerator rod is depressed and moves to the left (FIG. 5), it moves three dimensional cam 209 to the left toward the engine center line. Cam 209 has a surface bulge 211, which occurs every 180° around cam 209 and also varies in circumferential distance relative to longitudinal position. Cam follower roller 213 contacts bulge 211 as cam 209 rotates with rotation of shaft 215. Follower rod 217 connects in a manner described below to intake valve 155. In FIG. 5, follower rod 217 is shown rotated from its true position under and in back of three dimensional cam 209 so that the cam follower 213 shows functionally its contact with the cam 209 but not at its true angle, so its various parts can be visible. Then, it connects to rocker arm 219. The arm projects outward from pivot 221 that pivots between bracket arms 218 extending outward from housing 112. A second arm 223 also extends outward from pivot 221. Stem 225 of valve 155 attaches to the end of arm 223. Stem 225, which is seated by O-rings 226, extends through support 224
Valve face 227 engages seat 228 at the entrance of pre-compression cylinder 150 (FIG. 5). As bulge 211 moves follower rod 217 outward, the follower rotates arms 219 and 223 around pivot 221 to move valve 155 upward. For best performance two valves 155 yoked together would be used. As a result, the fuel/air mixture flows from intake manifold 154 into the pre-compression portion at the bottom of dual cylinder 150 (FIG. 4).
The fuel/air mixture flows into the bottom portion of dual cylinder 150 as dual piston 151 moves upward. The left to right position of three dimensional cam 209 changes the time that valve 155 remains open. The circumferential distance of bulge 211 is greater at the right end of cam 186 than at the left end (FIG. 5). Therefore, if accelerator rod 207 pushes cam 209 to the left, bulge 211 encounters roller 213 of the follower rod 217 for a greater part of the rotation of the cam. As a result, valve 155 remains open for a longer period of time allowing more fuel/air mixture to flow through the valve to be compressed.
As dual piston 151 moves downward, it forces the fuel/air mixture through opening 230 (FIG. 5), which is closed by reed valve 157. When the reed valve is open, the compressed fuel/air mixture flows from the bottom portion 198 (FIG. 5) of dual cylinder 150 through opening 230 and into channel 232. The channel extends to accumulator 104. Reed valve 157 only opens when the pressure in dual cylinder 158 is greater than the pressure in channel 230 and accumulator 104.
The fuel/air mixture next flows from accumulator 104 to the heat exchanger, which is not visible in FIGS. 4 and 5. From the heat exchanger, the cooled but compressed fuel/air mixture passes through ducts 124 and 134 into combustion chambers 128 and 138 (FIG. 4). Each combustion chamber 128 and 138 is generally conventional but smaller than conventional chambers because they receive a much denser fuel/air mixture. Both combustion chambers operate in a four cycle mode. In FIG. 4, only piston 121 is visible. The drawing does not show the inside of the other combustion chamber 138. Therefore, most of the continuing reference is made only with regard to combustion chamber 128.
Combustion chamber 128 has a piston 121 driven by piston rod 123, which is reciprocated by section 129 of crankshaft 101. The piston within combustion chamber 138 reciprocates 360° out of phase with drive piston 121 in combustion chamber 128. Piston 121 repeats its cycle of two upstrokes and downstrokes every 720° of crankshaft rotation.
Piston 121 reciprocates along cylindrical combustion chamber wall 120. Piston rings 129 prevent gases from flowing between the outside of piston 121 and cylindrical wall 120. The top face of piston 121 is domed or hemispherical. Means are provided for directing cool air through fins 252 and 182 for cooling combustion chamber wall 120.
Combustion piston 121 moves downward in combustion cylinder 120 pushing piston rod 123 downward against crankshaft section 129. Inlet valve 125 closes duct 124 leading from accumulator 104. Valve 125, and the four other valves that are described below are controlled by cams 235, 237, 239, 241 and 243. The five cams rotate with rotation of shaft 215 (FIGS. 4 and 5). Shaft 215 rotates through its connection with worm 233 (FIG. 4). A follower, only one of which, 245, is shown in FIG. 5, contacts the face of one of the cams. Radial movement of roller 245 moves cam rod 247 outward. By the appropriate connecting mechanism, each cam rod, such as cam rod 247, moves the appropriate valve, such as valve 125, inward.
Spring 246 (FIG. 4) pushes outward on valve 125. The pressure in inlet duct 124 leading from accumulator 104 may be very high. If, at that time, the pressure in combustion chamber 128 is relatively low, the pressure in duct 124 tends to unseat valve 125. Springs 264 maintain valve 125 in a seated condition unless the appropriate cam rod pushes valve 125 downward.
Valve head 189 of valve 157 closes the post-expansion chamber above dual piston 151. When valve 157 is open, exhaust gas passes into exhaust manifold 156. Valves 125, 127, 135 and 137 of combustion chambers 128 and 138 coordinate in one of two arrangements. In the first arrangement, valve 127 opens at the start and remains open during the expulsion stroke of the gas in chamber 128. Valve 157 opens before dual piston 151 reaches bottom dead center. The pre-compression stage occurs at the bottom side of piston 151 between piston face 191 and annular chamber wall 192. The downstroke of piston 151 provides the equivalent pre-compression that the upstroke piston 11 provides.
360° of crank rotation later, valve 137 of combustion chamber 138 also opens during the expulsion stroke of gas in the chamber, and valve 157 also opens slightly early near the end of the downstroke of its piston.
The pressure of the gas in chamber 128 can drop to atmospheric pressure through adjusting the timing of valves 127 and 157. As valve 127 closes, valve 125 opens and piston 121 begins movement away from head 122. The flow of fuel/air mixture from duct 124 into combustion chamber 128 exceeds the displacement that piston 121 normally produces. That is, the volume of residual exhaust gas from the previous cycle when piston 121 is at top dead center is much lower in pressure than the pressure in duct 124 and accumulator 104. The in-rush of the fuel/air mixture when valve 125 opens compresses any gas that remains in combustion chamber 128 until that gas is equal in pressure to the pressure of the fuel/air mixture in duct 124 and accumulator 224. The ratio of the inlet gas volume to the residual gas volume is approximately equal to the pre-compression ratio. Valve 127 is closed during the upstroke of piston 121 so that the gas does not flow into post-expansion chamber 158.
In the other method of operation, valve 127 closes before piston 121 completes its expulsion upstroke. Valve 127 closes when the gas in combustion chamber 128 will re-compress to the pressure of the gas in duct 124 and accumulator 104 at the end of the upstroke of piston 121. When the piston begins its downstroke and valve 125 opens, there is no appreciable, rapid flow of the fuel/air mixture from duct 124 past the valve into combustion chamber 128 because the pressures on both sides of the valve are approximately equal. Most of the work used to recompress the gas in combustion chamber 128 is returned as available work later in the cycle.
The volume of fuel/air mixture flowing into combustion chamber 128 during downstroke of piston 121 approximately equals the displacement of the piston. When piston 121 reverses and then reaches the top dead center position, the piston has compressed the fuel/air mixture in combustion chamber 128. A spark plug (not shown) then generates a spark to ignite the fuel/air mixture. The expanding gas acts on top face of piston 121 to create a downward force, which rotates crankshaft 101.
Duct 126 connects combustion chamber 128 with the top, post-expansion region 158 of cylinder 150. Piston 121 continues its expansion stoke to bottom dead center where the piston reverses its direction. Valve 127 opens at this point. At a set time (determined by the faces of one of cams 235, 237, 239, 241 or 243) during the upstroke, valve 127 closes and blocks flow from combustion chamber 128 into duct 126, thus completing the combustion chamber cycle. During this expansion, combustion products in chamber 128 are still above atmosphere pressure. If valve 157 closes before all of the gas in duct 126 reaches atmospheric pressure, trapped gas in the duct is recompressed so that the pressures in the duct and in dual chamber 158 is equal to the exhaust pressure in combustion chamber 128 (or 138) at about top dead center of dual piston 151. Also at top dead center of dual piston 151, section 171' (FIG. 4) extends into duct 126 to reduce the trapped volume of combustion products in ducts 126 and 136 (and 144) and post-expansion chamber 158. Valve 127 opens at about top dead center of dual piston 151. There is no sudden flow of gas past valve 127. When valve 127 opens, duct 126 provides a direct connection between chambers 128 and the top of dual chamber 158. When piston 121 moves upward and dual piston 151 moves downward, the total volume in the two chambers 128 and 158 above the two pistons 121 and 151 increases because the area of duel piston 151 is much greater than the area of piston 121. Just before piston 121 reaches its top dead center position, valve 127 closes. The total volume in ducts 126 and 144 and chamber 128 continues to increase as large piston 121 continues its movement toward bottom dead center. The cam mechanism opens valve 157 shortly before dual piston 151 reaches the bottom dead center position. When valve 157 is open, dual piston 151 expels gases at atmospheric pressure through duct 156.
The pressure of expanding gas acting on the face of dual piston 151 during its movement away from head 152 produces work 180° later than that produced by piston 121 and the other piston in combustion chamber 138. Energy is supplied to crankshaft 101 more evenly than two combustion chambers would supply without post-expansion in dual chamber 158. The multi-staged engine approaches the evenness of a conventional four cylinder engine.
Valves 127 and 137 may be pressure balanced valves. When dual piston 151 compresses gas in the top portion of post-expansion chamber 158, the rear face of valve 127 is exposed to high pressure. As a result, there is a tendency for valve 127 to open. To overcome this tendency, spring 248 can provide sufficient closing force, but it is difficult for the cam and rod to provide enough force to open the valve. Face 249 has an area slightly less than the area of the back 251 of the valve 127. The other side of face 249 is at atmospheric pressure, which provides a force that reduces the force that spring 248 would have to provide. Pressurized gas passes through opening 250 and pressurizes face 249 to balance approximately the differential pressure load in the opposite direction.
Finned cooling passages, such as passage 252, are provided on the outside of cylindrical walls 120 of the combustion chambers. Finned cooling passage 252 is representative. Cooling can be provided at other locations where it is necessary. Air for cooling can come from several sources. The exhaust gas in exhaust manifold 156 (FIG. 4) can drive a blower, ejector or other air flow device. The crankshaft may also be connected to an air compressor.
Applicant's teaching cam also be adapted to a compression ignition (diesel) version. FIG. 6 shows a representative exemplary embodiment of the compression ignition version. The FIG. 6 version also has more than one pre-compression stage. Although primarily adapted to the compression ignition version, two pre-compression stages with cooling after each could also be used with the spark ignition version of FIGS. 3 through 5.
Air from air intake 302 passes through intake duct 314 into first intake chamber 318 when crankshaft 301 reciprocates first pre-compression piston 311 during its movement in cylinder 310 away from head 312 (down in FIG. 6). Section 319 of crankshaft 301 rotates around the axis of the crankshaft between its top dead center position shown in FIG. 6, which corresponds to the closest movement of piston 311 toward head 312, and a bottom dead center position, which corresponds to the position of the piston farthest from head 312. Inlet valve 315 is open and outlet valve 317 is closed as crankshaft section 319 and piston rod 313 pull piston 311 downward.
As piston 311 moves down away from the head in first pre-compression chamber 318 and valve 315 is open, the air is drawn into the pre-compression chamber. Valve 315 may close when pre-compression piston 311 reaches its bottom dead center position, or the timing of its opening and closing may change in response to engine torque settings. Valve 317 remains closed.
Crankshaft section 319 continues to rotate from the bottom dead center position toward head 312 (up in FIG. 6) so that piston rod 313 pushes first pre-compression piston 311 toward the head to compress the air.
Outlet valve 317, which may be a reed valve or a controlled valve, opens when the pressure in first pre-compression chamber 318 is equal to the pressure in first accumulator 304. The compressed air flows past open valve 317 through duct 316 into the accumulator.
The air next flows from first accumulator 304 into first heat exchanger 306. A dividing plate 380 separates accumulator tank 382 into separate accumulators, first accumulator 304 and second accumulator 384. The compressed air flows through passage 374, which extends between heat exchanger 306 and dividing plate 380 past intake valve 375 into second pre-compression chamber 378. The second pre-compression stage operates similarly to the way in which the first pre-compression stage works. That is, crankshaft 301 rotates crankshaft section 379 so that piston rod 373 reciprocates second pre-compression piston 371 in cylinder 370. When piston 371 moves down away from head 372, it draws air from passage 374 past valve 375. Further rotation of crankshaft section 379 pushes piston 371 toward head 372 to further compress the working fluid. The working fluid is discharged past valve 377 into duct 376 and into second accumulator 384 when the pressure in pre-compression chamber 378 exceeds the pressure in second accumulator 384. Valves 375 and 377 are similar in operation and in related control structure to valves 315 and 317 of the first pre-compression stage, and all of them are similar to the respective valves 15 and 17 of the single pre-compression stage in the FIG. 3 embodiment.
The high pressure working fluid them passes through heat exchanger 386 where it can then flow to combustion chambers 328 and 338. Heat exchanger 386 is shown in the exemplary embodiment as a recuperator. The recuperator has a low pressure, hot fluid bypass valve 387, which controls the temperature of the high pressure working fluid from second accumulator 384 into combustion chamber 328 and 338. Valve 387 controls the amount of exhaust gas that flows through the other side of heat exchanger 386. By varying the position of valve 387, one can control whether the exhaust gases flow through heat exchanger 386 or bypass the heat exchanger as the gases flow from combustion chamber 348 past valve 347 into duct 346 and out exhaust 390.
Because of the ability to control the temperature of the working fluid that enters combustion chambers 328 and 338, the temperature can be sufficiently elevated so that further compression that the working fluid undergoes in the combustion chambers raises the working fluid temperatures to the point where compression ignition of the fuel will take place.
The ability to control the temperature allows the use of a wider range of possible fuels in this embodiment of the invention.
From the foregoing it should be apparent that the multi-staged engine of the pressure invention has the following advantages:
(1) Both the spark ignition and compression ignition versions of the multi-staged internal combustion engine are more efficient than existing internal combustion engines;
(2) Both the spark ignition and compression ignition versions of the multi-staged internal combustion engine can use a much wider range of fuels than can comparable existing engines;
(3) Both the spark ignition and compression ignition versions of the multi-staged internal combustion engine are smaller, lighter and warm up faster than comparable existing engines;
(4) The multi-staged spark ignition internal combustion engine has part load efficienices that are a much higher percentage of full load efficiency than do comparable present engines;
(5) The multi-staged spark ignition internal combustion engine produces much less pollution than do comparable present engines;
(6) The multi-staged spark ignition internal combustion engine varies torque of the engine over a very wide range of values much more efficiently than do comparable present engines which can make the transmission simpler and lighter and makes the vehicle easier to drive; and
(7) The multi-staged spark ignition internal combustion engine requires less energy to start than do comparable present engines so the batteries, starters, generators, wiring, etc. can be reduced in size and weight.
Because numerous modifications and alternate embodiments will occur to those skilled in the art, it is intended that the invention be limited only in terms of the appended claims.
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The positive displacement internal combustion engine has multiple stages of compression and expansion. After an initial compression, the working fluid is contained at elevated pressure and temperature. Valve controls on the initial compression can limit the thru-put of working fluid. Limiting the thru-put controls the pressure and density and as a consequence engine torque and power. A heat exchanger cools the working fluid before it enters a conventional spark ignition "combustion" cylinder. After the combustion of fuel in air in a conventional Otto or Diesel cycle the exhaust gas does further expansion in a post expansion stage. The efficiency benefits of the engine's high expansion ratio are realizable because of reductions in friction, fluid flow and heat transfer losses.
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CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Patent Application No. 61/218,160 filed on Jun. 18, 2009, the complete disclosure of which, in its entirety, is herein incorporated by reference.
GOVERNMENT INTEREST
The embodiments herein may be manufactured, used, sold, imported and/or licensed by or for the United States Government without the payment of royalties thereon.
BACKGROUND
1. Technical Field
The embodiments herein generally relate to electro-optic technology, and, more particularly, to electro-optic shutter devices.
2. Description of the Related Art
There are various types of conventional optical switches, each of which can be classified as either a passive optical switch or an active optical switch. Typically, a passive optical switch receives incoming light, and changes state based upon the received light. In this regard, some passive optical switches are semiconductors that employ two-photon absorption to activate, while other passive optical switches employ all-optical components and organic dyes. In contrast, active optical switches receive incoming light, and are activated and/or deactivated by a power signal.
Optical switches, as described above, are typically employed in telecommunications and fiber optic technologies, and may employ semiconductors or organic polymers. Typically, active optical switches are not employed to propagate images in a whole, un-encoded state, as this can easily be accomplished with a passive device. However, passive devices tend to suffer from several problems.
For example, although passive devices are inherently fast, their dynamic range is generally very limited, as there are only so many available molecules to respond. Thus, passive devices can saturate quickly. In addition, the fluence or irradiance threshold to turn a conventional passive device to the “on” state may be intolerably high, effectively preventing the device from performing its intended function.
Electro-optic shutters have a quick response time and good attenuation, but conventional active and passive shutters are generally unable to extinguish light evenly over the extent of the electro-optic element. Further, conventional devices are generally passive in nature, in that they use part of the incoming light transient to drive the device to a blocking state. This type of conventional construction has been found to be deficient in speed and effectiveness in blocking optical transients that would be harmful to a human eye or sensor.
SUMMARY
In view of the foregoing, an embodiment herein provides an electro-optic shutter comprising a first polarizer comprising a first polarizer face, and a second polarizer face positioned opposite the first polarizer face; a Pockels cell comprising a first cell face, a second cell face positioned opposite the first cell face, and an outer circumference disposed therebetween, wherein the first cell face of the Pockels cell is disposed adjacent to the second polarizer face of the first polarizer, and wherein the Pockels cell comprises a polymer material comprising a chromophore-doped copolymer or a guest-host polymer; a photo-conducting semiconductor switch (PCSS) in communication with the Pockels cell; a positive electrode in conductive communication with the PCSS; a negative electrode in conductive communication with the PCSS; and a second polarizer comprising a first face, and a second face positioned opposite the first face, wherein the first face of the second polarizer is disposed adjacent to the second cell face of the Pockels cell.
In one embodiment, the polymer material, which may be a poled sheet comprising one or more of a polycarbonate, amorphous polycarbonate, or polymethyl-methacrylate (PMMA) polymer host. In another embodiment, the chromophore-doped copolymer or guest-host polymer comprises one or more of coumarin and coumarin derivatives, or coumaromethacrylate-monomethacrylate copolymer, stilbene or tolane derivatives. Preferably, the chromophore-doped copolymer or guest-host polymer exhibits a linear electro-optic effect upon application of an electric field, the electro-optical activity being greater than approximately 10 pm/V. Furthermore, the chromophore-doped polymer or guest-host polymer preferably exhibits transmission in a visible range of approximately 400 to 700 nm. In another embodiment, the polymer material is optically active. Preferably, the PCSS reacts to light, wherein the light activates the Pockels cell causing it to discharge, and wherein the light-activated Pockels cell has an optical density of at least 3.0.
Another embodiment provides a method of manufacturing an electro-optic shutter device, the method comprising providing a transparent conducting electrode material; depositing a polymer sheet comprising a poling axis on the transparent conducting electrode material to form a polymer/electrode coated sheet having two layers of electrode material; heating the polymer/electrode coated sheet to a glass transition temperature of the polymer/electrode coated sheet; and folding the polymer/electrode coated sheet to form a consolidated unit, a Pockels cell having a poling direction, comprising interdigitated three dimensional electrodes to form the electro-optic shutter device.
Another embodiment provides a method of manufacturing an electro-optic shutter device, the method comprising providing a transparent conducting electrode material; depositing the transparent conducting electrode material on a poled polymer sheet comprising a poling direction, to form a coated polymer sheet having electrode material on a first side thereof, and a non-electrode side opposite the first side; cutting the coated polymer sheet into a plurality of approximately square pieces; bonding each approximately square piece to an adjacent approximately square piece at the non-electrode side to form a consolidated unit having a poling direction; planing and polishing the consolidated unit to transparency; disposing parallel vertical electrodes in the consolidated unit; depositing a common conductor upon the consolidated unit, a Pockels cell having a poling direction, to conductively connect all vertical electrodes to one another to form an electro-optic polymer Pockels cell; and bonding a photo-conducting semiconductor switch to the electro-optic polymer Pockels cell to form the fast shutter device.
Another embodiment provides a large-aperture direct-view high-speed electro-optic shutter includes an electro-optic polymer material forming a Pockels cell and an integrated photoconducting semiconductor switch. A chromophore-doped guest-host polymer material or chromophore-doped copolymer, wherein the chromophore is oriented within the polymer material, exhibits a linear electro-optic effect when an electric field is applied to the device. In one embodiment, the polymer host material comprises one or more of a polycarbonate, amorphous polycarbonate, or polymethylmethacrylate polymer hosts. The optically active chromophore comprising one or more coumarin and coumarin derivatives, stilbene or tolane derivatives is incorporated within the polymer host, forming a guest-host polymer. In another embodiment, the chromophore is chemically bonded to the monomer that forms the polymer, resulting in an optically active copolymer. The electro-optic shutter is then activated by incident light through the photoconducting semiconductor switch, rendering the electro-optic shutter opaque.
These and other aspects of the embodiments herein will be better appreciated and understood when considered in conjunction with the following description and the accompanying drawings. It should be understood, however, that the following descriptions, while indicating preferred embodiments and numerous specific details thereof, are given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the embodiments herein without departing from the spirit thereof, and the embodiments herein include all such modifications.
BRIEF DESCRIPTION OF THE DRAWINGS
The embodiments herein will be better understood from the following detailed description with reference to the drawings, in which:
FIG. 1 is a partial perspective view of a Pockels cell device according to an embodiment herein;
FIGS. 2A-C are an illustration of preferred chromophore compounds contained within a Pockels cell device according to an embodiment herein;
FIG. 3 is a modified index ellipsoid of an electro-optic polymer according to an embodiment herein;
FIG. 4 is an exploded perspective view of an electro-optic shutter device according to an embodiment herein;
FIG. 5 is a side view illustration of one method of manufacturing an electro-optic shutter according to an embodiment herein;
FIG. 6 is a side view illustration of an alternative method of manufacturing an electro-optic shutter according to an embodiment herein;
FIG. 7 is a side view illustration of a polishing step and PCSS connecting step involved in manufacturing an electro-optic shutter according to an embodiment herein;
FIG. 8 is a side view illustration of a polarizer bonding step involved in manufacturing a completed electro-optic shutter device according to an embodiment herein;
FIG. 9A is a top view of a completed electro-optic shutter device according to an embodiment herein;
FIG. 9B is a cross-sectional view of section A-A of the electro-optic shutter device of FIG. 9A according to an embodiment herein;
FIG. 10 is a front view of a conformable array comprised of a plurality of electro-optic shutter devices according to an embodiment herein;
FIG. 11 is a partial magnified view of the conformable array illustrated in FIG. 10 according to an embodiment herein;
FIG. 12 is a partial view of one quadrant of an assembled array of electro-optic shutter devices according to an embodiment herein;
FIG. 13 is a schematic diagram illustrating an example application of an electro-optic shutter device according to an embodiment herein; and
FIG. 14 is a circuit diagram of the circuit box of FIG. 13 according to an embodiment herein.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The embodiments herein, and the various features and advantageous details thereof, are explained more fully with reference to the non-limiting embodiments that are illustrated in the accompanying drawings and detailed in the following description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.
The embodiments herein provide an improved high-speed electro-optic shutter having a fast response time and good attenuation, while also being capable of extinguishing light evenly over the extent of the electro-optic element. Furthermore, the embodiments herein provide a Pockels cell based electro-optic shutter device capable of blocking optical transients to such an extent that damage to eyes and sensors does not occur. Referring now to the drawings, and more particularly to FIGS. 1 through 14 , where similar reference characters denote corresponding features consistently throughout the figures, there are shown preferred embodiments.
The Pockels effect is exhibited in chromophore-doped polymers. Specifically, certain crystals and polymers exhibit a linear electro-optic effect, such that birefringence occurs when the crystal is placed in an electric field. The induced birefringence is proportional to the applied electric field, and is due to the deformation of the indicatrix (index ellipsoid) due to the applied field. When a strong external electric field E is applied, the indicatrix is distorted; the length of the principal axes is modified and the orientation of the indicatrix is also modified as indicated:
κ′=κ+ r▪E (Eq. 1),
where r is the Pockels electro-optic tensor.
The indicatrix is renormalized to the new field. The form of a Pockels electro-optic tensor for a guest-host polymer of C ∞ν symmetry is shown in Equation (2) below. Such a material behaves as a uniaxial crystal. The Pockels electro-optic tensor is a third-rank tensor that is symmetrical in the first two indices, and generally contains 18 independent components. The C ∞ν symmetry reduces the number of independent components to two, since the non-vanishing components r 13 , r 23 , r 42 , and r 51 are all equal:
(
(
Δ
κ
)
1
(
Δ
κ
)
2
(
Δ
κ
)
3
(
Δ
κ
)
4
(
Δ
κ
)
5
(
Δ
κ
)
6
)
=
(
0
0
r
13
0
0
r
23
0
0
r
33
0
r
42
0
r
51
0
0
0
0
0
)
(
E
x
E
y
E
z
)
.
(
Eq
.
2
)
Prior attempts at creating large area Pockels-based shutter devices have used plasma electrodes and other contrivances to circumvent the problem of obscuration of the central aperture by the electrode. The requirement of a clear central aperture having low losses is due to the necessity of having lossless intracavity elements for a laser. As a fast shutter not used as a laser intracavity element, the large aperture direct-view Pockels devices face no such restriction.
The embodiments herein provide a novel Pockels cell device 100 , and an electro-optic shutter comprising such a Pockels cell device. The Pockels cell device of the embodiments herein comprises a chromophore-doped polymer. The Pockels cell device (i.e., the electro-optic element) operates as a half wave plate when a voltage V π is applied to the element, and has two opposing transverse surfaces. The chromophore-doped polymer is comprised of a polymer material, which acts as the substrate. In particular, the polymer material (i.e., the substrate) comprises, but is not limited to, one or more of a polycarbonate, amorphous polycarbonate, or polymethylmethacrylate (PMMA) polymer host. Preferably, the polymer is doped with, but is not limited to, one or more of coumarin and coumarin derivatives, stilbene or tolane derivatives in the form of a chromophore-doped guest-host polymer or chromophore-doped copolymer system.
In particular, as illustrated in FIG. 1 , a Pockels cell device 100 is provided, wherein the crystal axes are oriented as shown. The chromophore-doped polymer 101 contains oriented chromophores 102 , which exhibit a linear electro-optic effect (Pockels effect) under the influence of an applied electric field 104 . A new index ellipsoid is formed under the influence of the applied field 104 . The incident polarized light 103 propagates parallel to the x-axis 107 ; the y and z axes of the device 100 are shown as 106 and 105 , respectively.
As illustrated in FIGS. 2A-C , the oriented chromophores are preferably chromophores 210 , being specifically designed to have high electro-optical activity and transmission in the visible region, 400 to 700 nm. In FIG. 2A , the chromophore 210 is a coumarin derivative 211 , which is attached to the polymer 212 , polymethylmethacrylate (PMMA) resulting in a copolymer. In FIG. 2B , the chromophore is a stilbene derivative, specifically methoxynitrostilbene 213 and in FIG. 2C , the chromophore is a tolane derivative, specifically aminonitrotolane 214 . Alternatively, the chromophore may be simply dissolved in the polymer host, resulting in a guest-host system.
The incident polarized light 103 , as illustrated in FIG. 1 , polarized 45° to the z-axis 105 , can be resolved into two s and p polarized components, oriented 45° either side of the z-axis 105 of the poled polymer. One component is advanced by λ/4 and the other component is delayed by λ/4. The result is a total phase difference of λ/2, which rotates the incoming polarization 90° (illustrated as x-axis 107 ). The phase shift Δφ that occurs if light is passed through the poled polymer in the direction of the applied electric field is written as below:
Δφ=2π/λ 0 [n e −n o ]L (Eq. 3);
where Δφ is the phase shift (in radians) of the light of wavelength λ 0 (units of m); n o is the ordinary refractive index (dimensionless quantity) of the Pockels medium at wavelength λ 0 (units of m); n e is the extra-ordinary refractive index (dimensionless quantity) at wavelength λ 0 (units of m); r 33 and r 31 are the particular electro-optic constants for the Pockels material (units of m/V); and V is the applied voltage (units of V). The “half wave” voltage V π follows from the equation below:
V π =dλ 0 /L ( r 33 n e 3 −r 13 n o 3 ) (Eq. 4).
This voltage is on the order of several hundred volts to several kilovolts in a practical device, and scales in a linear fashion with wavelength. The modified index ellipsoid 200 is illustrated in FIG. 3 . The z, x and y axes are shown as 202 , 203 , and 204 , respectively. Under the influence of an applied field 205 , the original index ellipsoid 201 is modified to a new index ellipsoid 206 . The extra-ordinary axis (z-axis 202 ) is changed by ½n e 3 r 33 E ( 208 ) and the ordinary axis (y-axis 204 ) is changed by ½n e 3 r 13 E ( 207 ). The total effective change (from Equation (4)) is the difference r 33 n e 3 −r 13 n o 3 .
Examples of EO polymers with high EO coefficients are the Lumera DH series of chromophores based on a dialkoxythiophene type structure. The DH series of chromophores include DH6, DH10, DH13, DH28, all having EO coefficients>40 pm/V in a polycarbonate host. All these chromophore structures are based upon the 2′,2′-dicyanomethylen-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF) molecule. Various moieties on the TCF structure are altered to form the DH-series of materials.
Most research to date has focused on telecommunications applications requiring low loss and high EO coefficient at 1.3 to 1.5 μm. Some of these near-infrared materials may be suitable for this application when used in films less than 10 μm in thickness. However, the embodiments herein provide chromophore copolymer-doped polymer exhibiting a high transmission rate of from 400 to 700 nm, along with a high EO coefficient in excess of 10 pm/V.
The electro-optic shutter device 300 of the embodiments herein, as shown in FIG. 4 , comprises the above-described Pockels cell device 100 , is comprised of a first polarizer 304 having a first face, and a second face opposite the first face. The Pockels cell device 100 (i.e., the electro-optic element of an electro-optic shutter) has a first face, a second face opposite the first face, and an outer circumference disposed therebetween, the first face of the Pockels cell device 100 is disposed adjacent to the second face of the first polarizer 304 . The Pockels cell device 100 (i.e., the electro-optic element) operates as a half wave plate when a voltage V π is applied to the element, and has two opposing transverse surfaces.
A photo-conducting semiconductor switch (PCSS) 307 is disposed in communication with the Pockels cell device 100 . The PCSS 307 further is in conductive communication with a positive electrode 309 and a negative electrode 308 . Disposed adjacent to the second face of the Pockels cell device 100 is a second polarizer 310 having a first face, and a second face opposite the first face.
The first polarizer 304 is disposed adjacent to one transverse surface of the Pockels cell device 100 (i.e., the electro-optic element) and has a first transmission axis oriented 45° relative to the z-axis of the poled polymer. The second polarizer 310 is disposed adjacent to the other transverse surface of the Pockels cell device 100 (i.e., the electro-optic element) and has a second transmission axis 90° different than the first transmission axis. Each electrode 308 , 309 is disposed on one of the transverse surfaces of the Pockels cell device 100 (i.e., the electro-optic element), and has an electric field which is substantially uniform over the transverse extent of the Pockels cell device 100 (i.e., the electro-optic element).
Unpolarized light 301 propagating along axis 302 enters the first polarizer 304 with polarization axis 303 . Vertically polarized light 305 , corresponding with the n e axis 202 , shown in FIG. 4 , enters the Pockels cell device 100 . Part of the incident light activates the PCSS 307 . The PCSS 307 causes the negative electrode 308 and the positive electrode 309 to discharge the Pockels cell device 100 .
If the intensity of the polarized light 305 is insufficient to trigger the PCSS 307 , the light exits the Pockels cell device 100 as 45° polarized light 313 , and passes through the second polarizer 310 having a polarization axis 311 . However, if the intensity of the light 305 is sufficient to trigger the PCSS 307 to discharge the Pockels cell device 100 , the light exits the Pockels cell device 100 as polarized light 312 , which is 90° from the original polarized light 313 and is blocked by the second polarizer 310 having a polarization axis 311 . This configuration is embodied as a normally on or normally transparent device.
An example of a Pockels cell device 100 used in accordance with the embodiments herein may be manufactured as illustrated in FIG. 5 . In particular, a polymer sheet 401 , comprised of the chromophore-doped copolymer or guest-host polymer 101 of the embodiments herein, having a poling axis 402 , is deposited, in step 403 , on a transparent conducting electrode material 405 and 406 , such as, but not limited to, Indium Tin Oxide (ITO) or Baytron® conductive polymer, as non-limiting examples, so as to form a coated sheet 404 . Specifically, the coated sheet 404 has two layers of electrode material, 405 and 406 , respectively, deposited thereon.
Polymer sheet 401 is fabricated by dissolving a chromophore 210 in a suitable polymer 212 such as, but not limited to, PMMA. This mixing process is performed while the polymer 212 is heated above its glass transition temperature (T g ), the temperature at which the polymer becomes soft enough to accommodate the chromophore 210 . The resulting mixture is referred to as a guest-host polymer. The guest-host polymer remains heated above the glass transition temperature to allow forming by rollers, sheet extrusion, or other suitable polymer-melt processing technique to form a sheet of the desired thickness.
In the case of copolymers 212 - 214 , such as shown in FIGS. 2A-C , the copolymers are synthesized according to known techniques and heated above the glass transition temperature to allow forming by rollers, sheet extrusion, or other polymer melt processing technique to form a sheet of the desired thickness.
At this point, the polymer sheet 401 may be poled. In other words, the polymer sheet 401 has its constituent chromophore molecules aligned in the proper direction by the application of a high voltage electric field to folded structure 408 during step 407 . The high voltage is applied to the top and bottom surfaces of structure 408 to form a chromophore aligning field in the direction of arrow 409 . Alternatively, in process 419 , shown in FIG. 6 , the field is applied to structure 420 by applied positive and negative high voltage to alternate electrodes; i.e. even electrodes are negative and odd ones are positive. The resulting chromophore poling field 421 is perpendicular to the spacing of the electrodes.
The polymer/electrode coated sheet 404 is then heated to its glass transition temperature, as illustrated in step 407 in FIG. 5 . The resulting polymer electrode coated sheet 404 is then folded to form a consolidated unit 408 , having interdigitated three dimensional electrodes having a poling direction 409 .
Alternatively, as shown in FIG. 6 , the Pockels cell device 100 of the embodiments herein may be manufactured using process 410 , wherein a poled polymer sheet 411 , having poling direction 412 , has, in step 413 , a transparent conducting electrode material 414 , such as, but not limited to, Indium Tin Oxide (ITO) or Baytron® conductive polymer, as non-limiting examples, deposited thereon, so as to form a coated polymer sheet 415 . This poled polymer sheet 411 is comprised of the chromophore copolymer described herein. The coated polymer sheet 415 has an electrode material 414 on only one side thereof.
Then, in step 416 , the coated polymer sheet 415 is cut into a plurality of approximately square pieces 417 . The approximately square pieces 417 are then each bonded to the non-electrode side of the adjacent square piece, as illustrated by step 418 . The approximately square pieces 417 may be bonded to one another using cyanoacrylate cement, as a non-limiting example. However, any suitable conventional means of bonding may be used. Then, in step 419 , all of the approximately square pieces 417 are bonded together to form a consolidated unit 420 having poling direction 421 .
Consolidated unit 408 , as illustrated in FIG. 5 , and consolidated unit 420 , as illustrated in FIG. 6 , now enter the next step of the manufacturing process 430 , which is the planarization of the poled sheet as illustrated in FIG. 7 . In particular, consolidated unit 408 and consolidated unit 420 have both surfaces 431 and 432 planed and polished to transparency, as illustrated by step 433 . Through step 433 (i.e., the polishing process), both consolidated unit 408 and consolidated unit 420 end up with the same configuration. Then, in step 434 , the individual parallel vertical electrodes 437 of each individual approximately square piece 417 (shown in FIG. 6 ) are operatively connected by common conductors 435 . The resulting electro-optic polymer 436 may be poled at this step, if necessary. Then, in step 438 , the PCSS 307 is bonded and connected to the electro-optic polymer 436 to form the Pockels cell device 100 of the embodiments herein.
To form the completed electro-optic shutter device 300 of the embodiments herein, as shown in FIG. 8 , in process 440 , the first polarizer 304 is bonded to the Pockels cell device 100 using an optical adhesive 442 , by coating the optical adhesive 442 on the Pockels cell device 100 , and applying pressure to the first polarizer 304 in the direction shown. Similarly, the second polarizer 310 is bonded to the Pockels cell device 100 using an optical adhesive 444 , by applying optical adhesive 444 to the Pockels cell device, and applying pressure to the second polarizer 310 in the direction shown. The first polarizer 304 and the second polarizer 310 are oriented in a crossed configuration. Finally, in step 445 , curing to remove voids and bubbles is carried out to yield a finished electro-optic shutter device 300 .
As illustrated in FIGS. 9A and 9B , the electro-optic shutter device 300 of the embodiments herein is comprised of the Pockels cell device having the PCSS 307 bonded thereto. The dimensions A and B of the electro-optic shutter are variable, and determined by the application. In one non-limiting example, the dimensions A and B are on the order of 1 cm. Three-dimensional interdigitated electrodes 453 and 454 are connected to a high voltage source by pads 455 and 456 .
A cross-sectional view of the electro-optic shutter device 300 through A-A shows the thickness L (from Equation (4)), and is generally approximately millimeters, but may be tailored to the desired application. Likewise, the electrode spacing D is generally approximately, but not limited to, 0.5 to 1.0 mm, and may be tailored to the desired application. Light propagates through the device 300 in the direction shown through second polarizer 310 and first polarizer 304 .
As illustrated in FIG. 10 , in the general process 460 , a completed unit can be assembled in a mosaic-like fashion, by assembling a plurality of electro-optic shutter devices 300 together. In particular, in process 461 , the individual electro-optic shutter devices 300 are bonded to a suitable substrate, adjacent to one another, to form a conformable array 464 . The bonding can be accomplished using a silicone-based adhesive 462 or similar material. Preferably, the adhesive used is sufficiently rigid to support the deposition of electrically conducting strips 463 . The strips 463 carry the electrical charge necessary to operate the individual electro optic elements 300 . The individual electro-optic shutter elements 300 can be joined to form a curved element, if desired.
As illustrated in FIG. 11 , which is an expanded view of the array 464 of joined electro-optic elements cell shown in FIG. 10 , the electro optic shutter elements 300 are embedded in an insulating adhesive material 462 . The electrically conducting strips 463 in FIG. 10 are split into 473 and 475 as described in FIG. 11 . Ground common connector strip 473 carries an electrical charge via a smaller conducting strip 474 to the PCSS 307 . Another parallel strip, a positive common connector 475 , carries an opposite electrical charge to the opposing electrodes of the electro-optic shutter elements 300 via a strip 474 attached to a pad 476 . The connectors 473 and 475 are potted within the insulating adhesive material 462 , so as to protect the user against electrical shock.
FIG. 12 shows one quadrant of an assembled array 480 of electro-optic shutter devices 300 . The electro-optic shutter devices 300 are potted in an opaque electrically insulating polymer 487 that stabilizes the electro-optic shutter elements 300 against movement, and prevents unwanted light from passing around the electro-optic shutter elements 300 . Each row of electro-optic shutter elements 300 is connected electrically by a positive common connector 475 and common ground connector 473 . The common connectors 473 and 475 terminate in a positive pad 482 and ground pad 481 that allow electrical connection to the high voltage positive bus 486 and ground bus 485 . The connections to the positive high voltage bus 486 are accomplished by positive conducting strip 484 , and the connections to the ground bus are accomplished by ground conducting strip 483 . These conducting strips can be fabricated using known circuit board fabrication techniques.
FIG. 13 illustrates an example application of the electro-optic shutter device of the embodiments herein. In particular, in FIG. 13 , two completed lens assemblies (i.e., array 480 of electro-optic shutter devices) are attached to an eyeglass frame 491 . Two assemblies (i.e., array 480 ) are used to complete the device 490 . The completed optical device 490 may include opaque side shields or other desired aesthetic features. The positive and ground conducting buses 486 and 485 , as shown in FIG. 12 , are connected in parallel within the eyeglass frame 491 , terminating in one of the earpieces of the eyeglass frame 491 .
An insulated wire pair 493 connects the eyeglass frame 491 to a compact circuit box 492 . The circuit box 492 contains various circuit elements 500 , as shown in FIG. 14 , and contains an on-off switch 503 , a 9-volt battery connected to a commercially available compact high voltage power supply (not shown) applied to positive terminal 501 . The high voltage applied to terminal 501 passes through a charging resistor 502 and applies the high voltage to the electro-optic shutter elements 300 .
The resistor 507 allows the designer to tune the circuit for critically damped operation to maximize the efficacy of the device (i.e., device 490 of FIG. 13 ). The resistor 508 and inductor 509 are not actual discrete circuit elements, but describe the innate resistance and inductance contained within the electro-optic shutter element 300 . The elements of the PCSS 307 are contained within the electro-optic shutter element 300 as previously described. The elements of the PCSS 307 , when illuminated with light, cause the discharge of the electro-optic shutter element 300 to ground 505 , thus activating the device (i.e., device 490 of FIG. 13 ) as described above.
The Pockels cell device 100 provided by the embodiments herein operates with very fast electrical pulses (sub-nanosecond), and provides a significant advantage in speed over conventional mechanical shutters. Further, the device 100 provides for a higher attenuation than conventional passive chemical dye-based shutters. As discussed above, the Pockels cell device 100 provided by the embodiments herein may be incorporated in a thin, flexible electro-optic shutter device 300 composed entirely of a solid-state polymer.
The Pockels cell device 100 provided by the embodiments herein, as well as the electro-optical shutter device 300 comprising same, may be utilized in any application requiring very rapid blocking of an optical transient, including protection from damaging laser pulses from the millisecond regime to the nanosecond regime, and even to block pulses down to the femtosecond regime. In particular, the Pockels cell device 100 and electro-optical shutter device 300 provided by the embodiments herein provide excellent eye and sensor protection.
Those skilled in the art will recognize that the Pockels cell device 100 , the electro-optic shutter device 300 , and the method of manufacturing same, as provided by the embodiments herein, have many diverse applications and that the embodiments herein are not limited to the representative examples disclosed herein. Accordingly, the foregoing description of the specific embodiments will so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments 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. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the appended claims.
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A large-aperture direct-view high-speed electro-optic shutter includes an electro-optic polymer material constructed to form a Pockels cell and an integrated photoconducting semiconductor switch. A chromophore-doped polymer material or chromophore copolymer, wherein the chromophore is oriented within the polymer material, exhibits a linear electro-optic effect when an electric field is applied to the device. In one embodiment, the polymer host material comprises one or more of a polycarbonate, amorphous polycarbonate, or polymethylmethacrylate polymer hosts. The optically active chromophore comprising one or more coumarin and coumarin derivatives, stilbene or tolane derivatives is incorporated within the polymer host, forming a guest-host polymer. In another embodiment, the chromophore is chemically bonded to the monomer that forms the polymer, resulting in an optically active copolymer. The electro-optic shutter device is then activated by incident light through the photoconducting semiconductor switch, rendering the Pockels cell to have an optical density of at least 3.0.
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FIELD OF THE INVENTION
[0001] The present invention relates to an environmentally benign process for the simultaneous preparation of nanocrystalline anatase titanium dioxide and hydrazine monohydrochloride. In particular, the present invention relates to a process for the preparation of nanocrystalline anatase titanium dioxide and hydrazine monohydrochloride by reacting an aqueous solution of titanium tetrachloride taken in concentrated hydrochloric acid with hydrazine monohydrate under constant stirring at ambient temperature and pressure.
BACKGROUND OF THE INVENTION
[0002] Anatase titanium dioxide which is usually used as a photocatalyst removing environmental pollutants, as pigment material, additives for plastic product or for optical multi-coating reagent. Titanium dioxide has mainly three polymorphic forms of crystalline structure, that is anatase, brookite and rutile. The performance of titanium dioxide in various applications depends on its crystalline phase state, dimensions and morphology. Titanium dioxide with anatase phase has been used as a photocatalyst in different organic reactions. It is also used in photovolatics because of its high photoactivity. Titanium dioxide shows different electrical characteristics according to the oxygen partial pressure since it has wide chemical stability and non-stoichiometric phase region. Because of this it can also be used as a humidity sensor.
[0003] Impact of nanostructure on the properties of high surface area materials is an area of increasing importance for understanding, creating and improving materials for diverse applications. The synthesis of nanoparticles with controlled size and composition is of technological interest. Reference may be made to the chloride process commercialized by Du Pont in USA in 1956 for preparation of titanium dioxide powders by the chloride process wherein titanium tetrachloride vigorously reacted with air undergoing hydrolysis at 1000° C. The inherent disadvantage of the process is the use of high temperature and costly equipments to control the reactant mixing ratios and less control on the particle shape and size. Reference may be made to the sulfate process which was industrialized Titan company in Norway in 1916 wherein titanium sulfate is conventionally hydrolyzed at temperatures higher than 95° C. The disadvantage is the post calcination at 800-1000° C. to obtain the titanium dioxide powder.
[0004] The other chemical methods to obtain titanium dioxide powders include (a) hydrolysis with ammonium hydroxide solution (b) sol-gel method (c) hydrothermal synthesis (d) hydrodynamic cavitation etc.
[0005] The hydrolysis method suffers from the limitation that it necessitates a post-calcination of the precipitates of hydroxides to obtain the respective oxides. Reference may be made to US. Pat. No. 5,030,439 wherein a method is described to prepare particulate anatase titanium dioxide by reacting titanium tetrahalide with sulfuric acid at 65-100° C. to first form titanyl sulfate which is subsequently crystallized then re-dissolved in water and hydrolyzed at 85-100° C. to form titanium dioxide. The inherent disadvantage is that it is a two step process requiring subsequent heat treatment.
[0006] The conventional sol-gel method involves metal alkoxides which requires tight control of reaction conditions since alkoxides are intensely hydrolyzed in air.
[0007] Furthermore, the high price of alkoxides limits the commercialization of this process. Reference may be made to JP 9-124, 320 wherein the gel was formed by adding water to titanium tetrachloride dissolved in alcohol together with various kinds of acetates, oxalates and citrates containing alkali metals or alkaline earth metals. The inherent disadvantage is the use of expensive additives such as organic acids and needs a high temperature treatment after gel formation.
[0008] The hydrothermal synthesis needs high temperature and pressure conditions and hence requires the use of an autoclave. All the above wet chemical routes however involve a heat treatment either during the processing or as a post-calcination step. Reference may be made to the work of Bruno (U.S. Pat. No. 5,973,175, 1999) wherein titanium dioxide is prepared from amino titanium oxalate precursor by hydrothermal process. Reference may be made to U.S. Pat. No. 4,954,476 wherein a method to prepare a catalyst containing titanium dioxide as a primary ingredient in a hydrothermal process with meta- or ortho-titanic acid as starting material has been described. The inherent disadvantage of all the processes is the high temperature and pressure requirement. Reference may also be made to U.S. Pat. No. 3,242,557 wherein a process is described to prepare pigmentary titanium dioxide by hydrothermal precipitation. The inherent disadvantage is that during the reaction, the reaction mixture is subjected to ultrasonic vibrations.
[0009] Attempts to synthesize nanoparticles of oxides in particular include the above said chemical routes. But the inherent disadvantages are in controlling the agglomeration and particle growth, which is mainly caused because of the involved heat treatment. Attempts to use hydrazine hydrate are concentrated in obtaining metal nanoparticles like Silver where hydrazine hydrate is used as a strong reducing agent.
[0010] Reference may be made to the work of Pileni et al J. Phys. Chem. 1993, 97, 12974, wherein silver nanoparticles were prepared by reducing silver sulfosuccinate solution by hydrazine hydrate.
[0011] Hydrazine monohydrate has been used earlier to synthesize oxides like ferrites where hydrazine is used to form an intermediate which decomposes by self-ignition or self propagating high temperature synthesis to obtain the ultra fine powders of ferrites. In this context, reference may be made to the publications of Ravindranathan et. al J. Mat. Sci., 1986, 5, 221, wherein v-ferric oxide was prepared by thermal decomposition of hydrazine precursors in air around 200° C. Also reference may be made to the work by Suresh et. al. J. Thermal Anal., 1989, 35, 1137 wherein Magnesium ferrite has been prepared by the thermal decomposition of a metal oxalate hydrazinate precursor.
[0012] Reference may also be made to the work of Madhusudan Reddy et al., ( J. Solid Slate Chem., 2001, 158, 180 & Mater. Chem. Phys., 2002, 78, 239) wherein hydrazine monohydrate is used with titanium tetrachloride to obtain anatase titanium dioxide nanoparticles with 5-15 nm. The inherent disadvantage is that the precipitate was air dried at 80-100° C. followed by heat treatment at 300-400° C.
[0013] The main difference in the procedure adopted by Madhusudan Reddy et al. ( J. Solid State Chem., 2001, 158, 180 and Mater. Chem Phys., 2002, 78, 239) and the present invention for the synthesis of Nanoparticles of anatase titanium dioxide are the following.
1. Madhusudan Reddy et al obtained the crystalline Nanoparticles only after air drying the samples at 80-100° C. and then calcining at 300-400° C. 2. The Applicants' present conditions of temperature i.e., 20-40° C. and pressure around 1 atmosphere, and carrying out the reaction under nitrogen atmosphere; all of them result in Nanoparticles of anatase titanium dioxide unambiguously less than 5 nm; crystalline in nature with no heat treatment and calcinations.
Hydrazine monohydrochloride is a salt, which is obtained dissolved in the reaction medium, i.e., water. Freeze drying of the solution gives the salt in powder form. It is a deliquescent material hence the particle size cannot be obtained. However from XRD, the crystallite size can be estimated to be in the range of 15-20 nm.
[0017] The present invention discloses the preparation of nanocrystalline anatase titanium dioxide powder of particle size less than 5 nm reacting acidic aqueous titanium tetrachloride solution with hydrazine monohydrate at ambient reaction conditions in a single step without any subsequent heat treatment.
OBJECTS OF THE INVENTION
[0018] The main object of the present invention is to provide a convenient method for the preparation of nanocrystalline anatase titanium dioxide of particle size less than 1 to 5 nm in a single step process, which obviates the drawbacks as detailed above.
[0019] Another object of the present invention is to provide a method for the preparation of nanocrystalline anatase titanium dioxide powder at ambient conditions.
[0020] Yet another object of the present invention is to provide a method for the preparation of nanocrystalline anatase titanium dioxide powder without subjecting the reaction mixture to any heat treatment so as to prevent agglomeration.
[0021] Still another object of the present invention is to provide a process for the preparation of nanocrystalline anatase titanium dioxide powder of particle size less than 1 to 5 nm suitable for large scale preparation.
SUMMARY OF THE INVENTION
[0022] The novelty in the present invention is highlighted by the mechanism proposed for the formation of anatase titanium dioxide nanoparticles at room temperature from acidic aqueous titanium tetrachloride and hydrazine monohydrate. Hydrazine is a high energy compound having a positive heat of formation implying a high activity. The complete chemical equation for the process is formulated as:
TiCl 4 +HCl+5N 2 H 4 .H 2 O→TiO 2 +5N 2 H 4 .HCl+3H 2 O
[0023] Thermodynamic calculations for the Gibb's free energy (ΔG°) and heat of reaction (ΔH°) for the above equation have been found to be negative. The former indicates that the reaction is thermodynamically favorable and the latter suggesting the reaction is exothermic. It is this exothermicity which is responsible for the formation of anatase titanium dioxide nanoparticles at room temperature via a hydrazine complex formation. Since the reaction is instantaneous there is no noticeable increase in temperature of the reaction mixture. On the basis of the above equation, gravimetric analysis of the reactants and products gives a complete material balance with the mismatch of theoretical and practical yield less than 5% which justifies the technique to be termed as a ‘green route’.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The present invention relates to an environmentally benign process for the simultaneous preparation of nanocrystalline anatase titanium dioxide and hydrazine monohydrochloride from the acidic aqueous titanium tetrachloride solution by reacting with hydrazine monohydrate to form a titanium dioxide precipitate directly at ambient conditions of temperature and pressure in air.
[0025] Accordingly, the invention provides an environmentally benign process for the simultaneous preparation of nanocrystalline anatase titanium dioxide and hydrazine monohydrochloride which comprises preparation of nanocrystalline anatase titanium dioxide of particle size less than 1 to 5 nm by reacting acidic aqueous titanium tetrachloride solution with hydrazine monohydrate at ambient conditions in air.
[0026] In an embodiment of the present invention, nanocrystalline anatase titanium dioxide is prepared by a process which comprises (a) preparation of aqueous solution of titanium tetrachloride taken in concentrated hydrochloric acid, (b) step of reacting the above acidic aqueous solution with hydrazine monohydrate under constant stirring at ambient conditions in air to obtain the anatase titanium dioxide as precipitate (c) step of obtaining the anatase titanium dioxide powder by filtering the above obtained precipitate, washing with distilled water and drying at room temperature and (d) step of obtaining the hydrazine monohydrochloride by freeze drying the filtrate and washings. In another embodiment of the present invention, nanocrystalline anatase titanium dioxide is prepared in aqueous solutions in the temperature range of 20 to 40° C.
[0027] In yet another embodiment of the present invention, aqueous solutions of 5 to 40% (v/v) of titanium tetrachloride is used.
[0028] In still another embodiment of the present invention, the preparation of nanocrystalline anatase titanium dioxide is completed by bringing the reaction pH to 7-8 by the addition of hydrazine monohydrate.
[0029] The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present invention.
EXAMPLE-1
[0000] Preparation of Anatase Titanium Dioxide Nanoparticles
[0030] 20% titanium tetrachloride solution was prepared in concentrated hydrochloric acid. Aqueous solution of titanium tetrachloride was then prepared by taking 2 ml of the above solution in 100 ml distilled water. To the above aqueous acidic solution hydrazine monohydrate (99%) was added in the range of 10 to 99% v/v dropwise under constant stirring at normal temperature 30° C. and about atm. pressure. The pH of the solution was brought to 7 and stirred further for 30 minutes to obtain the anatase titanium dioxide as precipitate. The titanium dioxide precipitate was filtered, washed with distilled water for 15 times and dried at normal temperature in air. The byproduct hydrazine monohydrochloride was recovered by freeze drying the filtrate and washing the filtrate with water at a temperature in the range of −60-40° C.
[0031] The formation of anatase titanium dioxide nanoparticles was confirmed from the selected area electron diffraction pattern ( FIG. 1 ).
[0032] The particle size for titanium dioxide was found to be less than 3 nm using TEM ( FIG. 2 2 ).
[0033] The BET surface area of the as prepared anatase titanium dioxide powder was found to be 245 m 2 /g.
[0034] The byproduct hydrazine monohydrochloride recovered by freeze drying the filtrate and washings was confirmed by FT-IR[( FIG. 3 ).
[0035] The yield for both the product and byproduct was better than 95%.
EXAMPLE-2
[0000] Preparation of Anatase Titanium Dioxide Nanoparticles
[0036] 50% titanium tetrachloride solution was prepared in concentrated hydrochloric acid. Aqueous solution of titanium tetrachloride was then prepared by taking 2 ml of the above solution in 10 ml distilled water. To the above aqueous solution hydrazine monohydrate (99%) was added dropwise under constant stirring at 25° C. and about 1 atm. pressure. The pH of the solution was brought to 8 to obtain the anatase titanium dioxide as precipitate. The titanium dioxide precipitate was filtered, washed with distilled water for 10 times and dried at normal temperature in air. The byproduct; hydrazine monohydrochloride was recovered by freeze drying the filtrate and washings at −40° C.
[0037] The yield for both the product and byproduct was better than 95%.
[0038] The particle size for titanium dioxide was found to be less than 5 nm from TEM image ( FIG. 4 ).
[0039] The BET surface area of the as prepared anatase titanium dioxide powder was found to be 210 m 2 /g.
EXAMPLE-3
[0000] Preparation of Anatase Titanium Dioxide Nanoparticles
[0040] 20% titanium tetrachloride solution was prepared in concentrated hydrochloric acid. Aqueous solution of titanium tetrachloride was then prepared by taking 1 ml of the above solution in 10 ml distilled water in a round-bottom flask and degassed for 30 minutes by nitrogen purging. To the above aqueous solution hydrazine monohydrate (99%) was added dropwise under nitrogen atmosphere and constant stirring at 30° C. and about 1 atm pressure. pH of the solution was brought to 7 to obtain the anatase titanium dioxide as precipitate. The titanium dioxide precipitate was filtered, washed with distilled water for 10 times and dried at normal temperature in air. The byproduct hydrazine monohydrochloride was recovered by freeze drying the filtrate and washings at −40° C.
[0041] The formation of anatase titanium dioxide nanoparticles was confirmed from the selected area electron diffraction pattern.
[0042] The yield for both the product and byproduct was better than 95%.
[0043] The particle size for titanium dioxide was found to be less than 5 nm using TEM ( FIG. 5 )/)
[0044] The BET surface area of the anatase titanium dioxide powder was found to be 232 m 2 /g.
[0045] The main advantages of the present invention are:
1. It is an eco-friendly process for the preparation of nanocrystalline titanium dioxide in substantial amounts using hydrazine monohydrate. 2. It enables preparation of titanium dioxide nanoparticles in pure anatase form. 3. It is a single step process using commercially available titanium tetrachloride and hydrazine monohydrate without subsequent heating to higher temperatures. 4. It is suitable for large scale preparation of anatase titanium dioxide nanoparticles for commercial exploitation.
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The present invention relates to an environmentally benign process for the simultaneous preparation of nanocrystalline anatase titanium dioxide and hydrazine mohydrochloride, in substantial amounts from the acidic aqueous titanium tetrachloride solution by reacting with hydrazine monohydrate at ambient conditions of temperature and pressure. The process of the present invention is simple, easy to operate, pollution free, high in product purity and homogeneous in product particle.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to an apparatus for highly efficient coding of a digital image signal which is applied to a digital VTR or the like.
2. Description of the Prior Art
There have been known several highly efficient video signal coding methods whereby a mean bit length per pixel or a sampling frequency is reduced in order to fit the encoded signal into a narrower transmission band. The applicant of the present invention has already proposed highly efficient coding apparatuses in which a dynamic range which is specified by the maximum and minimum values of a plurality of pixels which are included in a two-dimensional block or a three-dimensional block is obtained and an encoding adapted to the dynamic range is executed (refer to JP-A-61-144989, JP-A-62-92620). Further, as disclosed in JP-A-62-128621, there has been proposed a variable length coding method in which a bit length used to represent data is changed in accordance with a dynamic range so that a maximum distortion due to quantization is set to be constant.
According to the adaptive dynamic range coding method (hereinafter, referred to as ADRC) which has been proposed above, the dynamic range DR (difference between the maximum value MAX and the minimum value MIN) is calculated for every two-dimensional block comprising, for instance, 64 pixels (=8 lines×8 pixels). The minimum level (minimum value) in the block is subtracted from each of the input pixel data. Each of the pixel data after the minimum value was subtracted is converted into a representative quantized level. The above quantization relates to processes for dividing the dynamic range DR which has been detected into four quantization level ranges corresponding to a bit length such as two bits which is smaller than the original unquantized bit length, for detecting the quantization level range to which each pixel data in the block belongs, and for generating a code signal indicative of the level range.
A highly efficient coding apparatus in which a three dimensional ADRC and a frame dropping process are combined in order to further raise a compression ratio has also been proposed by the applicant of the present invention. According to the above apparatus, motion between two areas of a three-dimensional block is detected, three-dimensional ADRC is executed in the block having motion, and in the stationary block, the transmission of one of the areas is omitted and two-dimensional ADRC is executed with respect to a block comprising a mean value of the two areas.
In the above apparatus in which the three-dimensional dimensional ADRC and the frame dropping process are combined, there is need for a memory capacity of two frames for a block segmentation process to form a three-dimensional block. When a buffering process is applied to the above apparatus, an additional memory of two frames is necessary to delay input data for a time until the number of bits to be assigned is decided by a buffering process. A memory capacity of two frames is also needed for a block desegmentation process in a decoding apparatus. As mentioned above, there is a problem in that the necessary memory capacity is extremely large.
OBJECTS AND SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a highly efficient coding apparatus in which high compression ratio can be achieved by a compression encoding such as ADRC or the like and frame dropping so that a required memory capacity is reduced.
According to an aspect of the present invention, there is provided an apparatus for highly efficient coding of a digital image signal, comprising:
means for converting the digital image signal into a block signal in which each frame of the digital image signal is arranged in a plurality of blocks of pixel data;
means for supplying a pixel data signal consisting of blocks of the blocked signal selected in response to a control signal;
control signal generating means for generating the control signal so that a first block of a first frame is always selected and a second block located in a spatially same position of a second frame as the first block occupies in the first frame is selected or dropped in accordance with an absolute value of a difference between values of pixel data at the same position in the first and second blocks; and
coding means for compression encoding the pixel data on a block unit basis.
According to another aspect of the present invention, there is provided an apparatus for highly efficient coding of a digital image signal, comprising:
means for converting the digital image signal into a blocked signal in which each frame of the digital image signal is arranged in a plurality of blocks of pixel data;
sub-sampling means for sub-sampling the blocked signal with a sub-sampling phase which is inverted at every two successive frames so as to produce a sub-sampled signal;
means for supplying a pixel data signal consisting of blocks of the sub-sampled signal selected in response to a control signal.
control circuit signal generating means for generating the control signal so that a first block of a first frame is always selected and a second block located in a spatially same position of a second frame as the first block occupies in the first frame is selected or dropped in accordance with an absolute value of a difference between values of pixel data at a same position in the first and second blocks; and
coding means for compression encoding the pixel data on a block unit basis.
The above, and other, objects, features and advantages of the present invention will become readily apparent from the following detailed description thereof which is to be read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1, 1A and 1B are diagram showing how FIGS. 1A and 1B are to be read together; FIGS. 1A and 1B together are block diagrams showing an embodiment of the present invention;
FIG. 2 is a schematic diagram which is used for explanation of a sub-sampling process;
FIG. 3 is a block diagram of the details of a buffering circuit shown in FIG. 1B;
FIG. 4 is a schematic diagram of a threshold value table;
FIG. 5 is a flowchart used for explaining of the operation of the buffering circuit;
FIGS. 6A and 6B are diagrams used for explaining a frequency distribution table formed by the buffering circuit of FIG. 3; FIG. 6B is a diagram used for explaining an accumulative frequency distribution table formed by the buffering circuit of FIG. 3;
FIGS. 7, 7A and 7B are flowcharts used for further explaining the operation of the buffering circuit; and
FIG. 8 is a diagram used for explaining the operation of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention will be described hereinbelow with reference to the drawings. The description will be made in the following order:
a. Whole apparatus
b. Buffering circuit
c. Explanation of the operation of an embodiment
d. Modification
a. Whole apparatus
In FIG. 1, (FIGS. 1A and 1B are herein referred to as FIG. 1) a digital video signal is supplied to an input terminal shown by reference numeral 1. The input digital video signal is supplied to a block segmentation circuit 2. The block segmentation circuit 2 converts the video signal arranged in a raster scan order into a blocked signal supplied in the order of the blocks. That is, a picture plane of one frame is segmented into two-dimensional blocks of, for instance, (4 lines×8 pixels). Different from a three-dimensional block, when a two-dimensional block is formed, the required memory capacity of the block segmentation circuit 2 can be reduced.
The blocked signal from the block segmentation circuit 2 is supplied to a sub-sampling circuit 3. The sub-sampling circuit 3 reduces the number of pixels into 1/2 by a quincunx sub-sampling pattern. Therefore, the number of pixels in one block in a sub-sampling signal output from the sub-sampling circuit 3 is equal to sixteen. A control signal to cause sub-sampling patterns of complementary forms every two frames is supplied from a terminal 4 to the sub-sampling circuit 3. Motion between the blocks can be detected from a difference of the pixel data of one frame by the sub-sampling.
FIG. 2 shows sub-sampling patterns. B1, B2, B3, . . . denote blocks which are located at a spatially same position and respectively belong to successive frames F1, F2, F3, . . . . A number of blocks other than the blocks shown in the diagram are included in each frame. In FIG. 2, ◯ and Δ denote transmission pixels and × indicates non-transmission pixels. In respective two frame periods of the frames F1 and F2 and the like, the sub-sampling patterns are the same. As shown by indicated by broken lines, the sub-sampling pattern of two frames and the pattern of the next two frames have complementary shapes.
The sub-sampling signal from the sub-sampling circuit 3 is supplied to a frame dropping circuit 5 which drops frames on a block unit basis, a comparing circuit 6, and a frame delay circuit 7. A control signal to control whether frames should be dropped or not, that is, to control the selecting or dropping of the blocks is supplied to the frame dropping circuit 5 through a switching circuit 8. The switching circuit 8 is controlled by a switching signal from a terminal 9 so as to alternately select input terminals a and b at one frame period.
A signal of "1" is always supplied to the input terminal a of the switching circuit 8. For the frame dropping circuit 5, "1" denotes that the block is selected for transmission. Therefore, the blocks B1, B3, B5, . . . included in the frames F1, F3, F5, . . . before two successive frames are circuit 8 is selected and the selecting or dropping of the blocks is adaptively controlled. That is, the selecting or dropping of the blocks is controlled on the basis of the absolute value of a frame difference between the preceding frame and the present frame.
The comparing circuit 6 detects a difference (namely, frame difference) between the values of the pixels of the present frame and the preceding frame. The frame difference is converted into an absolute value by an absolute value forming circuit 10. An output signal of the absolute value forming circuit 10 is supplied to a summing circuit 11. The absolute values among the frame differences with respect to every two pixels are summed by the summing circuit 11 for one block. An output of the summing circuit 11 is supplied to a comparing circuit 12.
A motion threshold value M is supplied to the comparing circuit 12 from a buffering circuit 19, which will be explained hereinlater. When the summed value is equal to or smaller than the threshold value M, an output of the comparing circuit 12 is set to "0". In the other cases, the output of the comparing circuit 12 is set to "1". In other words, when the summed value is equal to or less than the motion threshold value M, the frame dropping process in which the block is dropped is executed. The data corresponding to the motion amount between the blocks can alternatively be formed by a method other than that shown in the present embodiment.
The output of the comparing circuit 12 to control the selecting or dropping of the block is also supplied to a detecting circuit 20 in order to detect a transmission ratio w. The detecting circuit 20 detects a transmission ratio w for one frame period. Since the adaptive frame dropping is executed in the frames F2, F4, . . . after every two frames, a transmission ratio w of the data to be transmitted to the original data changes in each frame after the two frames. Since the total number of blocks in one frame is known, a ratio of the number of blocks which are transmitted to the total number is detected as a ratio w. An output signal of the detecting circuit 20 is supplied to the buffering circuit 19. The output signal of the detecting circuit 20 is also necessary to indicate the block which has been frame-dropped at the reception side and is supplied as a frame dropping flag to a frame segmentation circuit 22 and is transmitted together with various encoding data, which will be explained hereinlater.
An ADRC encoder is connected to the frame dropping circuit 5. The buffering circuit 19 is provided as part the encoder.
An output signal of the frame dropping circuit 5 is supplied to a detecting circuit 13 and a delay circuit 14. The detecting circuit 13 detects the dynamic range DR and the minimum value MIN of the block. The delay pixel circuit 14 delays data to enable detection of the minimum value MIN and the dynamic range DR. The subtracting circuit 15 subtracts the minimum value MIN from each of the pixel data from the delay circuit 14, so that the pixel data from which the minimum value has been subtracted are supplied from the subtracting circuit 15.
The output data of the subtracting circuit 15 and the dynamic range DR are supplied to a quantizing circuit 18 through delay circuits 16 and 17, respectively. An encoded signal DT of an n-bit length (n=0, 1, 2, 3, or 4 bits) smaller than the original bit length (8 bits) is obtained from the quantizing circuit 18. The quantizing circuit 18 executes quantization adapted to the dynamic range DR. That is, the pixel data from which the minimum value has been subtracted is divided by a quantization step Δ which is obtained by dividing the dynamic range DR into 2" equal steps. An integer value which is obtained by omitting a fraction of the quotient is used as a code signal DT. The quantizing circuit 18 can be constructed of a dividing circuit or a ROM.
A bit length n which is assigned to the code signal DT is determined in a manner such that an amount of data generated per predetermined period, for instance, every two frames does not exceed a target value L (bits). For such a buffering, the buffering circuit 19 to which the dynamic range DR is supplied is provided. A plurality of, for example, 32 sets (T1, T2, T3, T4, M) of threshold values are prepared for the buffering circuit 19 as will be explained hereinlater. The sets of the threshold values are distinguished by parameter codes Pi (i=1, 2, 3, . . . , 32). The amount of data generated is set so as to monotonically decrease as the number i of the parameter code Pi increases. However, the picture quality of the reconstructed image deteriorates with a decrease in the amount of data generated.
The threshold values T1 to T4 for the quantization level divisions from the buffering circuit 19 and the dynamic range DR which has been transmitted through the delay circuit 17 are supplied to a bit length deciding circuit 21. The delay circuit 17 is provided to delay the dynamic range data by a time which is required to decide the quantization level threshold values by the buffering circuit 19. The dynamic range DR and the quantization level threshold values T1 to T4 (T1<T2<T3<T4) are supplied to the bit length deciding circuit 21. The bit length n to be used is determined on the basis of the magnitudes of the dynamic range DR and the threshold values T1 to T4.
The encoded outputs DR, MIN, and DT of the ADRC encoder, the flag indicative of the selecting or dropping of the block, and the parameter codes Pi are supplied to the frame segmentation circuit 22. The transmission data is supplied therefrom to an output terminal 23. The frame segmentation circuit 22 forms the transmission data by adding a sync signal to the above encoded outputs. The frame segmentation circuit 22 also appends an error correction code to the above encoded outputs.
Although not shown, on the receiving side, there are provided a frame desegmentation circuit, an ADRC decoder, a circuit to interpolate the frame dropped block from the preceding block, a circuit to interpolate the pixels where were not transmitted, a block desegmentation circuit, and the like. The ADRC decoder decodes the bit length n using the threshold values T1 to T4 which are designated by the parameter codes Pi and the dynamic range DR and reconstructs the pixel data value by using the quantization step Δ according to the bit length n and the dynamic range DR and the value of the code signal DT. Further, the minimum value MIN is added to the reconstructed level.
b. Buffering circuit
FIG. 3 shows an illustrative embodiment of the buffering circuit 19. A memory (RAM) shown by reference numeral 31 is provided for the buffering circuit 19 in order to form a frequency distribution table and an accumulative frequency distribution table. An address is supplied to the memory 31 through a multiplexer 32. The dynamic range DR is supplied as one input of the multiplexer 32 from an input terminal 33 and an address from an address generating circuit 41 is supplied as another input. An output signal of an adding circuit 34 is supplied to the memory 31. Output data of the memory 31 and an output of a multiplexer 35 are added by the adding circuit 34.
An output of the adding circuit 34 is supplied to a register 36. An output of the register 36 is supplied to the multiplexer 35 and a comparing circuit 37. In addition to the output of the register 36, 0 and +1 are supplied to the multiplexer 35. When calculation of an amount of data generated has been performed, a generation data amount l i for one frame period generated by ADRC encoding is obtained in an output of the register 36.
The comparing circuit 37 compares the generation data amount l i and a target value from a switching circuit 38. An output signal of the comparing circuit 37 is supplied to a parameter code generating circuit 39 and a control signal generating circuit 48. The parameter codes Pi from the parameter code generating circuit 39 are supplied through a switching circuit 40 to the address generating circuit 41 and a register 42. The parameter codes Pi taken into the register 42 are supplied to the frame segmentation circuit 22 as mentioned above and are also supplied to an ROM 43. A table of threshold values shown in FIG. 4 has been stored in the ROM 43. The ROM 43 generates sets (T1i, T2i, T3i, T4i, Mi) of the quantization level threshold values in correspondence to the parameter codes Pi which have been input as addresses. The threshold value table is constructed so as to more severely limit the amount of data generated as the number of the parameter code Pi increases. That is, the values of the quantization level threshold values T1 to T4 and the motion threshold value M monotonically increase. As mentioned above, the quantization level threshold values are supplied to the bit length deciding circuit 21 and the motion threshold value M is supplied to the comparing circuit 12.
The transmission ratio w which has been detected by the detecting circuit 20 is supplied to an arithmetic operating circuit 45. Assuming that a target value for the generation data amount for a two-frame period of time of F1 and F2 or the like is set to L, the arithmetic operating circuit 45 executes an arithmetic operation of L/(1+w). The result of the arithmetic operation is supplied to a comparing circuit 46. An output of the arithmetic operating circuit 45 is used as a target value for the present frame when the mean value of the numbers of the sets of the threshold values for the preceding two-frame period is used as data for the present frame.
A generation data amount l' transmitted through a register 47 is supplied to the comparing circuit 46. A comparison output of the comparing circuit 46 is supplied to a control signal generating circuit 48. The generation data amount l' is derived with respect to the present frame when the mean value of the numbers of the sets of the threshold values for the preceding two-frame period is used as data for the present frame. The generation data amount l' is also supplied to a subtracting circuit 49. The subtracting circuit 49 subtracts l' from a target value L for the 2-frame period. (L-l') from the subtracting circuit 49 is supplied to an input terminal d of the switching circuit 38. A target value of L/2 is supplied to the other input terminal c of the switching circuit 38.
The output signal of the comparing circuit 46 is supplied to the control signal generating circuit 48.
The control circuit 48 generates control signals to clear the registers 36, 42, 47, and 50, a signal to control the fetching of the data into the register 42, and switching signals to respectively control the switching circuits 38 and 40. The switching circuit 38 supplies the target value of L/2 to the comparing circuit 37 through the input terminal c in the initialized state and upon detection of a scene change. In the other cases, the switching circuit 38 supplies an output signal of the subtracting circuit 49 to the comparing circuit 37 as a target value.
The parameter codes Pi from the parameter code generating circuit 39 are supplied to an input terminal e of the switching circuit 40, a register 50, and an adding circuit 51. An output of the register 50 is supplied to the adding circuit 51. An output of the adding circuit 51 is supplied to a 1/2 multiplying circuit 52. The mean value of the parameter codes Pi and Pi+1 indicative of the averaged threshold value of two successive frames is generated from the 1/2 multiplying circuit 52. The mean value is supplied to an input terminal f of the switching circuit 40. The switching circuit 40 is controlled by the switching signal from the control signal generating circuit 48. When the terminal e of the switching circuit 40 is selected, the parameter codes Pi from the parameter code generating circuit 39 are supplied to the address generating circuit 41. On the other hand, when the input terminal f is selected, the mean values of the parameter codes Pi and Pi+1 indicative of the averaged threshold values are supplied to the address generating circuit 41.
In the illustrated embodiment, in the initiatized state or just after a scene change occurs, buffering to control an amount of data which is generated for one frame period to be L/2 or less is executed. That is, in the above case, as shown in FIG. 3, the switching circuit 38 selects the input terminal c and the switching circuit 40 selects the input terminal e. The operation of the buffering circuit 19 in this state will now be described with reference to a flowchart of FIG. 5.
In the first step 61, the memory 31 and the registers 36, 42, 47, and 50 are cleared to zero. To clear the memory 31 to 0, the multiplexer 32 selects the address generated from the address generating circuit 41 and the output of the adding circuit 34 is always set to 0. The address is incremented to (0, 1, 2, . . . , 255) and 0 data is written into all of the addresses in the memory 31.
In the next step 62, a frequency distribution table for the dynamic range DR of the blocks of a current frame in a period of time when buffering is executed is formed in the memory 31. The multiplexer 32 selects the dynamic range DR for each of the blocks in the frame from the terminal 33. The multiplexer 35 selects +1. Therefore, at the end of one frame period, the generation frequency of each DR for each of the blocks in the frame is stored into each address in the memory 31 corresponding to the dynamic range DR. In the frequency distribution table in the memory 31, an axis of abscissa indicates the DR and an axis of ordinate represents the frequency as shown in FIG. 6A.
The frequency distribution table is converted into the accumulative frequency distribution table (step 63). When the accumulative frequency distribution table is formed, the multiplexer 32 selects the address from the address generating circuit 41 and the multiplexer 35 selects the output of the register 36. The address is sequentially decreased from 255 to 0. The read-out output of the memory 31 is supplied to the adding circuit 34 and is added to the content in the register 36 by the adding circuit 34. The output of the adding circuit 34 is written into the same address as the read address of the memory 31. The content in the register 36 is updated to the output of the adding circuit 34. In the initial status in which the address in the memory 31 is set to 255, the register 36 has been cleared to 0. When the frequencies have been accumulated with respect to all of the addresses in the memory 31, an accumulative frequency distribution table as shown in FIG. 6B is formed in the memory 31.
A generation data amount l i when the sets (T1i, T2i, T3i, T4i) of the quantization level threshold values have been applied to the accumulative frequency distribution table is calculated (step 64). To calculate the generation data amount l i, the multiplexer 32 selects the output of the address generating circuit 41 and the multiplexer 35 selects the output of the register 36. The parameter code generating circuit 39 generates a parameter code which sequentially changes from P1 to P32. The parameter codes Pi are supplied to the address generating circuit 41 through the switching circuit 40 and the addresses corresponding to the threshold values of (T1i, T2i, T3i, T4i) are sequentially generated.
Values A1, A2, A3, and A4 which have been read out of the addresses corresponding to the threshold values are accumulated by the adding circuit 34 and the register 36. The accumulated value (A1+A2+A3+A4) corresponds to the generation data amount l i when the sets of the threshold values designated by the parameter codes Pi have been applied. That is, in the accumulative frequency distribution table shown in FIG. 6B, a value in which the number (16) of pixels in the block has been multiplied to the total value (A1+A2+ A3+A4) of the values A1, A2, A3, and A4 which had been read out of the addresses respectively corresponding to the threshold values T1, T2, T3, and T4 is equal to the generation data amount (bit length). Since the number of pixels is constant, multiplying by the number of pixels is omitted in the buffering circuit 19 shown in FIG. 3.
The generation data amount l i is compared with the target value L/2 (step 65). The output of the comparing circuit 37 which is generated when li≦L/2) is satisfied is supplied to the parameter code generating circuit 39. The incrementing of the parameter code Pi is stopped. The parameter code Pi is stored in the register 42. The parameter code Pi from the register 42 and the set of the threshold values from the ROM 43 are generated (step 66).
If (l i≦L/2) is not satisfied in discriminating step 65 in the comparing circuit 37, the parameter codes Pi are incremented to the next parameter codes Pi+1 and the address corresponding to Pi+1 is generated from the address generating circuit 41. In a manner similar to the above, a generation data amount l i+1 is calculated, used as the new 8i, with the target value L/2 by the comparing circuit 37. The above operations are repeated until (l i≦L/2) is satisfied.
c. Explanation of the operation of an embodiment
The operation of the embodiment will be described with reference to FIG. 7. In an initiatized state in which the image data of the first frame F1 shown in FIG. 2 is input, buffering to reduce the amount l 1 of data which is generated for the frame F1 L/2 or less is executed, as described above in conjunction with FIG. 5. The two-dimensional ADRC encoding is executed using the quantization level threshold values T1 to T4 at that time (step 71). N1 denotes the number of the threshold value used in the frame F1, that is, the number i which coincides with the parameter code Pi of the threshold value used.
In the next frame F2, the frame dropping process is executed on a block unit basis using the motion threshold value M indicated by N1 (step 72). The transmission ratio w2 of the frame F2 after completion of the frame dropping process is detected by the detecting circuit 20 (step 73). The data of the frame F2 after completion of the frame dropping process is ADRC encoded (step 74). The threshold value at that time is set so as to reduce the generation data amount L 2 to L/2 or less in a manner similar to the frame F1.
With respect to the frames F1 and F2, the target value L for the 2-frame period is set to one half of its value, thereby setting the target value L/2 for the one frame period. For the frame F2, however, an amount of data to be transmitted is reduced by sub-sampling. Thus, as shown in FIG. 8, the number N1 of the threshold value for the frame F1 is large and the number N2 of the threshold value for the frame F2 is fairly small.
After an accumulative frequency distribution table was formed with regard to the next frame F3, a generation data amount l 3' when the encoding has been executed by the mean value N3 of the numbers N1 and N2 of the threshold values of the two preceding frames F1 and F2 is obtained (step 75). The generation data amount l 3' is supplied to the comparing circuit 46 through the register 47. The comparing circuit 46 executes a comparing operation of (l 3'≦L/(1+w2)) (step 76).
When the above relation is satisfied, the data of the frame F3 is encoded using the quantization level threshold value indicated by the number N3 (step 77). On the contrary, when the above relation is not satisfied, it is determined that a scene change has occurred. The buffering so as to reduce the generation data amount l 3 regarding the frame F3 to L/2 or less is performed and the data of the frame F3 is encoded using the threshold value determined by the buffering (step 81). the above process is similar to that used in the initialized state in step 71. The operations similar to those in step 71 and subsequent steps are repeated hereinbelow.
When the relation in step 76 is satisfied, the frame dropping process for the frame F4 is executed using the motion threshold value M3 indicated by the number N3 of the threshold value (step 78). A ratio w4 of the transmission data of the frame F4 after the frame dropping is detected (step 79).
In the buffering for the frame F4, (L-l 3') formed by the subtracting circuit 49 is used as a target value. That is, in the preceding frame F3, since the amount of data l 3' has been generated for the target value L for the 2-frame period, the amount of data generated in the frame F4 is constrained to a value which is equal to or less than the remaining target data amount of (L-l 3'). The data of the frame F4 is encoded using the threshold value indicated by the number N4 determined by the buffering (step 80). The next process of step 80 is similar to that in step 75 and processes similar to those mentioned above are repeated.
In the embodiment in which the above operations are executed, when the scene change does not occur, as shown in FIG. 8, the number indicating the set of threshold values converges to a mean value shown by a broken line for the frame F3 and subsequent frames.
d. Modification
In the above description, the dynamic range DR and the minimum value MIN are transmitted in order to describe the dynamic range information. However, the maximum value MAX or the quantization step width can be alternatively be transmitted in place of the dynamic range DR.
On the other hand, in the above embodiment, the encoding process has been applied to the pixel data themselves of the block after each 2-frame period. However, the encoding can be also performed on a difference (residual) between each pixel data of the preceding frame and each pixel data of the next frame. That is, in such a case, the data corresponding to the pixels in each block of the next frame has differential value.
The invention, further, can use a block encoding of a DCT (Discrete Cosine Transform) or the like other than the foregoing ADRC. In the case of the DCT, the encoding using the above differential value in place of the pixel data is effective.
According to the invention, since the ADRC compression encoding or the like is executed for a two-dimensional block, the necessary memory capacity can be reduced as compared with a three-dimensional block. On the other hand, since a hybrid construction is used combining frame dropping on a block unit basis and compression encoding, the compression ratio can be raised.
Having described a specific preferred embodiment of the present invention with reference to the accompanying drawings, it is to be understood that the invention is not limited to that precise embodiment, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope or the spirit of the invention as defined in the appended claims.
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An apparatus for highly efficient encoding of a digital image signal comprising frames of pixels converts the digital image signal into a blocked signal, sub-samples the blocked signal to reduce the number of pixels in each block by one-half and then performs adaptive dynamic range coding (ADRC) and frame dropping on the sub-sampled signal. The ADRC compresses the amount of pixel data in a first frame to half of a two-frame target value by subtracting the minimum value of the pixels in a block from each of pixels in the block, then representing each of the resultant pixel data values with a smaller number of bits than was originally used. This smaller number is determined based on the dynamic range of the block and the target value. A second frame following the first frame is dropped if it is detected as a stationary frame, or is compressed using ADRC to the two-frame target value reduced by the amount of data generated for the first frame if detected as a non-stationary frame.
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[0001] This application claims benefit of U.S. Provisional Patent Application Ser. No. 61/235,460, filed on Aug. 20, 2009. The teachings of U.S. Provisional Patent Application Ser. No. 61/235,460 are incorporated herein by reference in their entirety.
BACKGROUND OF THE INVENTION
[0002] Large bore reinforced hose can be utilized in a wide array of applications. One important application for large bore reinforced hose that is of growing importance in the world today is in loading and unloading oil tankers and floating production storage and offloading units (FPSOs). Such hose has an inside diameter of 5 cm or greater and typically has an inside diameter ranging from 20 cm to 80 cm. Such hose for offshore applications is also typically designed to include a floatation medium to provide the hose with sufficient buoyancy so that it will float on the surface of water. Hose for offshore applications typically has reserve buoyancy when filled with sea water which is within the range of 10% to 40%. A reserve buoyancy of at least 20% is frequently demanded by customers. Because vast reserves of petroleum are located under water in many locations around the world including under the North Sea, the Gulf of Mexico, off the coast of Brazil, and off the coast of California there is a growing demand for large bore reinforced floating hose.
[0003] Transferring the crude oil from FPSOs to shuttle tankers at sea is an extremely demanding task because of the persisting relative movement between the vessels. During times of adverse weather conditions, such as high waves, high winds, and storms at sea, this tack becomes even more difficult. Floating hoses typically run from the bow and/or the stern of FPSOs to shuttle tankers. Modern shuttle tankers may have a bow manifold for charging crude oil, but many conventional shuttle tankers have a charging device consisting of a midship manifold for intake of the oil load. For this reason a relatively long loading hose is needed, from the FPSO-vessel to the midship manifold on the shuttle tanker. The separation between the vessels, between the stern of the FPSO and the bow of the shuttle tanker is generally about 50 to 200 meters, and the extension of the floating hose is normally between about 150 and 300 meters.
[0004] When the floating hoses are not being used to transfer petroleum they can be allowed to remain floating on the water after being released from the tankers. However, in such cases where the floating hose is left on the water the floating hose may be damaged by being struck by ships, sea creatures or by the movement from waves in stormy weather. In any case, hose wear occurs due to continual wave action. This can lead to a loss of the buoyancy and/or primary carcass failure and over time the hose can begin sink.
[0005] In the alternative, the floating hose can be hoisted onto the FPSO for storage until it is again needed for offloading crude oil to a shuttle tanker. This can be done by using a wench to pull the floating hose onto a reel. This protects the hose from exposure to waves and the inherent wear associated therewith. It also eliminates the danger of the floating hose being struck by a ship as it is floating at sea. However, pulling the hose onto a reel puts the couplings that connect different sections of hose under a tremendous amount of stress. At the point where the coupling is being pulled onto the reel it experiences a particularly high level of stress and compressive forces. Over time, these forces can cause the hose to fail at or near the point where it is attached to a coupling. In any case, large bore reinforced hoses are prone to failure at their couplings. This is also the case where large tensile loads are encountered in catenary and deep water submarine applications.
[0006] Today, there is a need for couplings for large bore reinforced hoses that are more resilient and which are capable of being incorporated into hoses that are more durable and capable of being repeatedly pulled onto reels and more resilient to high tension and bending loads. It would accordingly be desirable to develop couplings for large bore reinforced hoses that are more resistant to failure and which have a longer service under harsh service conditions, such as being repeatedly pulled onto reels.
SUMMARY OF THE INVENTION
[0007] The hose couplings of this invention can be used to connect sections of large bore reinforced hose to make them more resistant to damage and to provide longer service life. These couplings can be used in conjunction with virtually any reinforced hose and are particularly beneficial when used in conjunction with hose that has a propensity to being damaged by virtue of being subjected to axial and bending forces, such as those encountered while being spooled on a reel. More specifically, hose utilizing the couplings of this invention is not as susceptible to being damaged or destroyed by the forces normally encountered during normal usage. This extends the service life of hoses of this invention which include such couplings.
[0008] The present invention more specifically discloses a coupling for a large bore hose, said coupling comprising a tubular body which is adapted for fitting into the end of said large bore hose, said tubular body having a tail end which is adapted to lie inwardly from the end of the hose, said tubular body having an outer end which is adapted to extend beyond an axial end of the hose, and at least one hose carcass anchor which is affixed to the tubular body, wherein the carcass anchor is adapted for the hose carcass and/or load bearing extensions of the carcass to extend through and/or around the carcass anchor.
[0009] The subject invention also reveals a coupling for a large bore hose, said coupling comprising a tubular body which is adapted for fitting into the end of said large bore hose, said tubular body having a tail end which is adapted to lie inwardly from the end of the hose, said tubular body having an outer end which is adapted to extend beyond an axial end of the hose, the outer surface of said tubular body being provided with a plurality of axially spaced retention beads, and at least one hose carcass anchor which is affixed to the tubular body at a point on or outward from the last retention bead toward the outer end of the tubular body, wherein the carcass anchor is adapted for the hose carcass and/or load bearing extensions of the carcass to extend through and around the carcass anchor.
[0010] The present invention further discloses a hose assembly comprising a reinforced hose having at least one reinforcement layer and a coupling on at least one end of the hose, said coupling comprising a tubular body which is adapted for fitting into the end of said large bore hose, said tubular body having a tail end which is adapted to lie inwardly from the end of the hose, said tubular body having an outer end which is adapted to extend beyond an axial end of the hose, and at least one hose carcass anchor which is affixed to the tubular body, wherein the hose carcass and/or load bearing extensions of the hose carcass are affixed to the carcass anchor. For instance, load bearing extensions of the hose carcass which are comprised of steel wire or cable can be welded or clamped onto the carcass anchor. Fabric or polymeric cords or fibers can also be clamped onto the carcass anchor or wound around and/or through it. Virtually any attachment means that is capable of securely affixing the load bearing extensions of the hose carcass to the carcass anchor can be used.
[0011] The subject invention also reveals a hose assembly comprising a reinforced hose having at least one reinforcement layer and a coupling on at least one end of the hose, said coupling comprising a tubular body which is adapted for fitting into the end of said large bore hose, said tubular body having a tail end which is adapted to lie inwardly from the end of the hose, said tubular body having an outer end which is adapted to extend beyond an axial end of the hose, and at least one hose carcass anchor which is affixed to the tubular body, wherein the hose carcass and/or load bearing extensions of the hose carcass extend through and/or around the carcass anchor.
[0012] The subject invention further reveals a hose assembly, sometimes referred to as the “hitching post assembly,” comprising a reinforced hose having at least one reinforcement layer and a coupling on at least one end of the hose, said coupling comprising a tubular body which is adapted for fitting into the end of said large bore hose, said tubular body having a tail end which is adapted to lie inwardly from the end of the hose, said tubular body having an outer end which is adapted to extend beyond an axial end of the hose, the outer surface of said tubular body being provided with a plurality of axially spaced retention beads, and at least one hose carcass anchor which is affixed to the tubular body at a point on or outward from the last retention bead toward the outer end of the tubular body, wherein the hose carcass and/or load bearing extensions of the hose carcass extend through and around the carcass anchor.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a cross sectional illustration of the coupling of this invention which is attached to the end of a hose.
[0014] FIG. 2 is a view of the hose helix anchoring to a fitting ring with fabric.
[0015] FIG. 3 is a first view illustrating anchoring a second set of main reinforcements to a ring.
[0016] FIG. 4 is a second view illustrating anchoring a second set of main reinforcements to a ring.
[0017] FIG. 4 a also illustrates the embodiment of the invention shown in FIG. 4 with a series of anchoring fabrics being shown as extending through a series of slots in the coupling before they are folded back upon themselves and cured into the hose carcass in the manufacturing process.
[0018] FIG. 5 illustrates a coupling having a carcass anchor which is a plurality of pins that extend radially from the tubular body of the coupling.
[0019] FIG. 6 is a cutaway view showing a coupling having a carcass anchor which is a plurality of pins that extend radially from the tubular body of the coupling with the carcass and reinforcing fabric extending through and around the carcass anchor.
[0020] FIG. 7 is a first view that illustrates a coupling with an anchoring helix to fitting with steel cable.
[0021] FIG. 8 is a second view illustrates a coupling with an anchoring helix to a fitting with steel cable.
[0022] FIG. 9 is a third view illustrates a coupling with an anchoring helix to a fitting with steel cable.
[0023] FIG. 10 is a first view illustrating an anchoring helix to a fitting with steel bars.
[0024] FIG. 11 is a second view illustrating an anchoring helix to a fitting with steel bars.
[0025] FIG. 12 illustrates an anchoring helix to a fitting ring with a chain.
DETAILED DESCRIPTION OF THE INVENTION
[0026] The couplings of this invention can be beneficially used in conjunctions with hoses of different sizes and that are designed for a wide variety of purposes. However, the couplings of this invention are of particular benefit for use in conjunction with large bore hoses having an inside diameter of at least 5 cm and which typically has an inside diameter ranging from 20 cm to 80 cm and an outside diameter which is within the range of about 40 cm to about 150 cm, such as floating hose that is used in transferring crude oil and other liquids over water (in filling and unloading tanker ships), catenary systems and deep water submarine applications.
[0027] The couplings of this invention can be used in conjunction with floating hose having a carcass with an inside and an outside, a floatation medium surrounding the hose carcass and an outer cover. They may also be used in a single carcass hose that is either designed for floating, submarine applications or as a catenary system. This type of floating hose typically has an inside diameter which is within the range of about 30 cm to 80 cm and an outside diameter which is within the range of about 40 cm to about 150 cm. For instance, many commercial floating hoses of this type have an inside diameter of 50 cm (20 inches) and an outside diameter of 95 cm (38 inches).
[0028] The carcass is of a tubular shape and is typically comprised of a base submarine hose complete with end fittings. The hose carcass is surrounded by a floatation medium which is typically comprised of several layers of closed cell foam. The closed cell foam can be multiple layers of a polymeric foam, such as polyurethane or polyethylene foam. The floatation medium will have a density and a total volume that is sufficient to provide the floating hose 1 with a reserve buoyancy when filled with sea water which is within the range of 10% to 40%. The floating hose will more typically have a reserve buoyancy when filled with sea water which is within the range of 15% to 35%. In most cases the floating hose will have a reserve buoyancy when filled with sea water of about 25%. In fact, many specifications call for a reserve buoyancy of at least 20%.
[0029] The floating hose includes a carcass and can optionally include a second carcass to attain a higher level of safety, performance and better durability. The hose carcass is typically comprised of a cured rubber which can be reinforced with a polymeric fabric, such as nylon or polyester, and/or steel reinforcements. For instance, the hose carcass can be reinforced with Kevlar® aramid fiber. The hose carcass will typically be comprised of a cured rubber, such as natural rubber, synthetic polyisoprene rubber, styrene-butadiene rubber (SBR), polyneoprene rubber, styrene-isoprene rubber, polybutadiene rubber, styrene-isoprene-butadiene rubber, nitrile rubber, carboxylated nitrile rubber, ethylene-propylene-diene monomer rubber (EPDM), or a mixture thereof. The hose carcass will also typically include one or more liners. To provide desired levels of chemical resistance such liners will generally be comprised of a nitrile rubber. To attain excellent heat resistance, oil resistance, and chemical resistance fluoroelastomers, such as Viton® fluoroelastomer, can be used in making the liners as well as thermoplastic liners such as crosslinked polyethylene.
[0030] The floatation medium can be provided by wrapping multiple layers of closed cell foam around the hose carcass. A thin layer of rubber is preferably laid between the carcass and the floatation medium. The floatation medium will normally be about 6 cm to about 18 cm thick. In other words, the floatation medium will extend outwardly from the carcass about 6 cm to about 18 cm. The floatation medium will preferably be about 10 cm to about 15 cm thick and will most preferably be about 12 cm to about 14 cm thick.
[0031] The floatation medium is surrounded outwardly with the outer cover of the hose. The outer cover is normally comprised of textile breakers with a rubber cover (a textile reinforced rubber cover). The outer cover can optionally include a polyurethane coating. In any case, the outer cover is designed to contain and protect the floatation medium from water damage and environmental conditions.
[0032] FIG. 1 shows a coupling of this invention which is attached to the end of a hose to make a hose assembly 1 . In this illustration the hose 2 is used in conjunction with the coupling to make a hose assembly 1 . The coupling includes a tubular body 3 , a tail end 4 , an outer end 6 , a first retention bead 7 , a second (last) retention bead 8 , and a carcass anchor 9 . Such couplings can contain more than two beads and/or one or more anchors if desired. On the other hand, in some applications it may be desirable for the coupling to contain no retention beads or only a single retention bead. In the embodiment of the invention shown in FIG. 1 the end of the hose 5 , including the hose carcass 10 and reinforcing fabric therein, extends around and through the carcass anchor 9 . The carcass anchor 9 can be a series of pins that extend radially from the tubular body 3 . The term pins as used in this context is intended to include bolts, rods or bars that extend radially outwardly from the tubular body of the coupling. The carcass anchor 9 can also be a ring that is affixed to the tubular body through a plurality of rods or plates that extend outwardly from the tubular body to the ring. In another embodiment of this invention, the carcass anchor 9 is in the form of metal wires or cables, such as steel wires or cables, that are attached directly to the coupling and which extend into the hose carcass. In most cases reinforcing elements within the hose carcass, such as reinforcing fabric and/or cords, will extend through and/or around the carcass anchor.
[0033] FIG. 2 illustrates a hose helix anchored to a fitting ring with fabric. In this figure, the anchoring fabric 11 extends through and around the fitting ring 12 and anchors the hose helix wire 13 which is spirally wrapped around the carcass to the tubular body of the hose. The flange 14 of the coupling is conventional and used to connect multiple hoses together through fitting 15 which is anchored to the carcass 16 of the hose via the anchoring fabric 11 which is interwoven through and around the helix wire 13 . Accordingly, FIG. 2 illustrates one embodiment of the subject invention wherein a carcass anchor, in this case the anchoring fabric 11 , is used as a load bearing extension which extends through and around a carcass anchor which in this case is fitting ring 12 .
[0034] FIG. 3 illustrates another anchoring mechanism wherein the main body reinforcement 17 is anchored to a fitting ring 18 with fabric 19 which is the main reinforcement that runs the full length of the hose. In this figure, the fabric 19 extends through and around the fitting ring 18 and anchors the main body reinforcement 17 which is spirally wrapped around the carcass to the tubular body 20 of the hose. The flange 21 of the coupling is conventional and can be used to connect multiple hoses together through fitting 22 which is anchored to the carcass of the hose via the anchoring fabric 19 which is attached to or a part of the main body reinforcement 17 . Accordingly, FIG. 3 illustrates one embodiment of the subject invention wherein a carcass anchor, in this case the anchoring fabric 19 , is used as a load bearing extension which extends through and around a carcass anchor which in this case is fitting ring 18 . FIG. 4 illustrates an alternative embodiment in which supplemental fabric strips 23 are used to anchor the main body reinforcement 17 . In this embodiment of the invention the supplemental fabric strips can be of any length and do not necessarily extend throughout the entire length of the hose. FIG. 4 a shows another view of the embodiment illustrated in FIG. 4 wherein the fabric strips 23 extend through a series of slots 48 in the coupling retaining ring 49 . The illustration shown in FIG. 4 a depicts the coupling in one step of its manufacturing process before the fabric strips are folded back upon themselves and cured into the hose carcass as illustrated in FIG. 4 . It should be noted that the fabric strips can optionally be wrapped around helix wires or can be simply folded or cured into the body of the hose.
[0035] FIG. 5 illustrates a coupling 24 having a carcass anchor which consists of a plurality of pins 25 which extend radially from the tubular body 26 of the coupling 24 which includes a flange 26 which is adapted for attaching the hose to other hose segments. FIG. 6 shows a coupling for a large bore hose which has the coupling illustrated in FIG. 5 attached thereto. In this embodiment of the invention the body of the coupling 27 has a multitude of pins 25 radially affixed thereto wherein the reinforcement fabric 28 is wrapped around the pin 25 and secured with binding wires 29 . The helix wires 30 are situated past the pins 25 toward the flange end of the hose 31 to further secure the hose carcass to the coupling.
[0036] FIG. 7 illustrates a large bore hose having a coupling in accordance with one embodiment of this invention. In this embodiment of the invention the coupling 32 is anchored to the hose carcass 33 through an anchoring wire 34 which is interwoven through the helix wire 35 and secured to the coupling 32 . In this embodiment the anchoring wire 34 extends over a bead of the hose carcass 36 . FIG. 8 illustrates a specific embodiment for anchoring the anchoring wire 34 to the coupling 32 . In this particular embodiment the anchoring wire 34 extends through a series of holes 37 (only one hole is shown in this figure) in the coupling 32 and is bent back on itself and secured with a clamping device 38 . Typically, a series of anchoring wires are affixed to the coupling by being passed through a multitude of holes in the coupling. FIG. 9 illustrates a further means for affixing the anchoring wire 34 to the coupling 36 which involves passing the anchoring wire 34 through a pipe 39 which is affixed to the coupling 36 via a secure attachment means (such as through a weld). Normally, a series of pipe segments 39 are attached to the coupling to facilitate affixing a multitude of anchoring wires to the coupling. As can be seen in this embodiment of the invention the anchoring wire 34 is woven through the helix wires 35 as previously explained.
[0037] FIG. 10 and FIG. 11 illustrate still another embodiment of this invention. In this embodiment a series of steel strips 40 are securely affixed to the coupling 41 by an effective means such as being welded. The steel strips 40 are formed to conform with beads 42 and other structural irregularities of the hose. The steel strips are affixed to the helix wire 43 by some effective attachment means such as a series of welds.
[0038] FIG. 12 illustrates still another embodiment of this invention. FIG. 12 shows the coupling 44 without the body of the hose being shown. In this embodiment of the invention steel chains which are comprised of a series of chain links 45 are used as the carcass anchor. The chains are attached to the coupling 44 either through welding or by being run through a series of holes in the coupling. The chain links are then affixed to the hose carcass (not shown) by passing the helix wires 46 through the chain links 45 . The coupling 44 , of course, includes a conventional flange 47 for attaching the hose to a fluid inlet or outlet or another hose.
[0039] The key to this invention is providing the coupling with anchors that allow the hose carcass or a load bearing extension of the carcass to extend through and around the anchors. This allows for the stress associated with tensile loading to be delivered directly to the coupling through the carcass anchors rather than through the interface between the hose and the tubular body of the coupling as is the case with the coupling designs of the prior art. The carcass anchors will normally extend into the hose no further than the cement line behind the first retention bead. In many cases, the carcass anchors will not extend into the hose as far as the first retention bead.
[0040] In one embodiment of this invention the carcass anchor is a plurality of pins that extend radially from the tubular body. In another embodiment of this invention the carcass anchor is a ring which is affixed to the tubular body through a plurality of rods or plates that extend outwardly from the tubular body to the ring. The outer surface of the tubular body is provided with at least one retention bead. For instance, the outer surface of the tubular body can include two retention beads or a plurality of axially spaced retention beads. The carcass anchor is attached to the tubular body at a point on or outward from the retention bead toward the outer end of the tubular body.
[0041] The reinforcing fabric of the hose carcass can extends through and/or around the carcass anchor. In on embodiment of this invention the carcass anchor is a plurality of pins that extend radially from the tubular body. In another embodiment of this invention the carcass anchor is a ring which is affixed to the tubular body through a plurality of rods or plates that extend outwardly from the tubular body to the ring. Typically, the hose assembly will be void of longitudinal supports. The carcass wire can be a metal wire or cable, such as a steel wire or cable, which is directly attached to the coupling.
[0042] The outer surface of the tubular body is typically provided with at least one retention bead and can include two retention beads. In some cases, it may be desirable for the outer surface of the tubular body of the coupling to include a plurality of axially spaced retention beads. The carcass anchors are normally situated outwardly toward the end of the hose from the first retention bead. For instance, the carcass anchors are situated outwardly toward the end of the hose from the cement line behind the first retention bead. Normally, the carcass anchor is attached to the tubular body at a point on or outward from the last retention bead toward the outer end of the tubular body.
[0043] While certain representative embodiments and details have been shown for the purpose of illustrating the subject invention, it will be apparent to those skilled in this art that various changes and modifications can be made therein without departing from the scope of the subject invention.
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The hose couplings of this invention can be used to connect sections of large bore reinforced hose to make it more resistant to damage that can be caused by axial and bending forces encountered during normal usage. This extends the service life of the hoses of this invention which include such couplings. The present invention more specifically reveals a hose assembly comprising a reinforced hose having at least one reinforcement layer and a coupling on at least one end of the hose, said coupling comprising a tubular body which is adapted for fitting into the end of said large bore hose, said tubular body having a tail end which is adapted to lie inwardly from the end of the hose, said tubular body having an outer end which is adapted to extend beyond an axial end of the hose, the outer surface of said tubular body being provided with a plurality of axially spaced retention beads, and at least one hose carcass anchor which is affixed to the tubular body at a point on or outward from the last retention bead toward the outer end of the tubular body, wherein the hose carcass and/or load bearing extensions of the hose carcass extend through and around the carcass anchor.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation in part of our application Ser. No. 285,159, filed Aug. 31st, 1972, now abandoned.
FIELD OF THE INVENTION
The present invention is concerned with improvements in or relating to emulsifying agents produced by microbiological processes.
REVIEW OF THE PRIOR ART
There has been a constant search for new emulsifying agents in view of the many valuable ways in which they can be used. One example of such a use is in the dispersal of oil spills on sea and land, the emulsifying action of the agent considerably enlarging the surface area of the spilled material to correspondingly increase the natural rate of oxidation and biodegradation. Such use of an emulsifying dispersant on a large spill is extremely expensive and many of the most readily available materials have unknown or even toxic effects upon the local flora and fauna.
DEFINITION OF THE INVENTION
It is the principal object of the present invention to provide new emulsifying agents which are of microbiological origin.
It is a more specific object to provide such new agents which are particularly suitable for the emulsification of high carbon fuels such as kerosene and Bunker C oil.
In accordance with the present invention there is provided a process for the production of an emulsifying agent of microbiological origin comprising the step of cultivating by an aerobic fermentation in aqueous solution and with paraffinic hydrocarbon substrate as principal source of assimilable carbon a microorganism of species Corynebacterium hydrocarboclastus of the type UWO 419 or NRRL-B-5631 until the fermentation medium contains at least 0.1% by weight of an active emulsification agent consisting of an extra-cellular polymer formed as a result of the fermentation.
Also in accordance with the invention there is provided an emulsifying agent of microbiological origin consisting essentially of the extra-cellular polymer product of an aqueous aerobic fermentation employing a microorganism of species Corynebacterium hydrocarboclastus with paraffinic hydrocarbon substrate, the said polymer comprising a polysaccharide component including primarily galactose, glucose and mannose in the ratio about 1:2.65:1.96 and a bound protein component, the polymer containing about 1 to 4% by weight organic nitrogen and about 30 to 35% by weight carbohydrate.
Preferably the said extra-cellular polymer comprises a polysaccharide component including galactose, glucose and mannose.
Preferably the molecular weight of the product is greater than 20,000.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In a process for producing an emulsifying agent in accordance with the invention the culture Corynebacterium hydrocarboclastus, the taxonomic description of which is given below, is cultivated with a long chain paraffinic hydrocarbon substrate in a suitable aqueous nutrient medium.
The nutrient medium consisted of a solution in tap water of the following by weight:
______________________________________ NaNO.sub.3 0.5% K.sub.2 HPO.sub.4 0.5% Yeast extract 0.3% KH.sub.2 PO.sub.4 0.2% MgSO.sub.4 0.2% NaCl 0.1%______________________________________
Under laboratory conditions about 15 liters of this solution were added to a 24 liter fermentation vessel, together with about 5% by volume of culture inoculum and about 1.5% by weight of kerosene. The pH of the contents was adjusted to 6.5 - 6.8. The temperature was controlled at 28° ± 0.5° C, aeration was supplied by bubbling air therethrough at 5 liter/min., while the contents were agitated vigorously by an impeller operating at 500 r.p.m. A standard plot of cell growth against time gives a sigmoid curve with the exponential phase completed in 60 hours.
The fermentation broth itself may be used as an emulsifying agent in accordance with the invention, and may be freeze dried directly for storage purposes, or the active principle comprising an extracellular polymer that accompanies the cell formation may be separated from the broth. In a typical separation any unused kerosene is removed from the broth by extraction with ether or chloroform, and thereafter the cellular component is removed by centrifuging (e.g. at 10 - 12,000 r.p.m. in a Sorvall centrifuge for 30 - 60 mins.) The cellular mass is dried overnight and weighed to determine yield.
The impure polymer also is effective as an emulsification agent and may be recovered from the supernatent liquid of the centrifugate by precipitation at pH 3.0 - 6.5 with two or more volumes of alcohol, acetone or similar solvents. The polymer is soluble in water and weak or strong acids or bases. The precipitation starts at pH 5.0 and no precipitation occurs at pH 7.0.
If desired the polymer can be purified by redissolving in water, if necessary, dialysation with water and subsequent removal of low molecular weight contaminants, particularly those with molecular weight less than 20,000 by first filtration through a Millipore filter of 1.2 μ and 0.45 μ pore size and then by use of an ultra filter with Diaflo membrane PM-30 or XM-50. The purified agent is reprecipitated and the solvent removed under vacuum at slightly elevated temperature, or by use of dry heat at temperatures less than 130° C.
The synthesis of the extracellular polymer appears to be associated quantitatively directly with that of the cellular material, so that cell growth must be increased to obtain higher polymer production.
The production of cellular material obtained was 10 - 13 grams/liter, which corresponds to a yield of 67 - 87% by weight of hydrocarbon supplied, while the polymer was produced at 5.0 - 6.0 grams/liter, which corresponds to 37 - 40% by weight of the hydrocarbon. The rate of cell production in an exponential phase was 0.27 g/liter hr., while the corresponding rate of polymer formation was 0.25 g/liter hr.
The polymer emulsifying agent component possesses many characteristics of a polysaccharide but it also contains a bound protein component. The polymer contains 1 - 3% organic nitrogen as determined by Kjeldahl by the method described by Welcher (1962). The carbohydrate content is 30 - 35% as determined colorimetrically using anthrone reagent and expressed as glucose equivalent (Morris, 1948). Hydrolysis of the polymer yields 0.015% phosphorus as determined colorimetrically using stannous chloride reagent. The polysaccharide component consisted of galactose, glucose and mannose in the ratio 1:2.65:1.96, traces of arabinose and xylose and a hexuronic acid expressed as glucuronic acid equivalent. All have been identified by paper chromatographic techniques and gel filtration. Monomers were identified by spraying with p-anisidine hydrochloride (Hough et al, 1950), 1.0% potassium permanganate in 2.0% sodium carbonate (Pascu et al, 1949), benzidine (Horrocks, 1949) and glucuronic acid using naphtharescorcinol reagent (Hawk et al, 1951).
The amino acid content of the protein part of the polymer was determined from acid hydrolysate (100° C, 24 hr. in 5.7 N HCl, sample hydrolyzed in 60%) by use of an automatic amino acid analyzer. In addition, many were identified by paper chromotography. These are summarized in Table 1 below.
TABLE 1______________________________________ % IN HYDROLYZED PROTEIN______________________________________AMINO ACID SAMPLE 1 SAMPLE 2______________________________________aspartic acid 12.20 11.44threonine 7.91 7.61serine 8.36 8.74glutamic acid 10.34 9.68glutamine 1.91 2.60proline 2.39 2.50glycine 14.19 13.28alanine 13.16 12.56cystine trace tracevaline 1.81 1.98methionine 4.68 5.33isoleucine 2.89 2.95leucine 7.63 7.65tyrosine 2.56 2.83phenylalanine 3.15 3.51histidine 3.10 3.76ornithine 0.70 0.55lysine 3.02 3.03arginine trace trace______________________________________
INFRA-RED ANALYSIS
Highly purified polymer was subject to infra-red analysis. The polymer was purified by continued dialysis through a Diaflo membrane XM50 ultrafilter, the remaining emulsifying agent having a mol. wt of approximately 50,000 was freeze dried and analyzed by IR using the KBr pellet method. The spectrum is shown in Table 2 along with a tabular interpretation.
The spectra indicates the emulsifier is a complex material of a high molecular weight containing phosphate, amino nitrogen, carboxyl and hydroxyl groups.
TABLE 2______________________________________Approximate Position of Vibrating Groups Most ProbablyBands Maximum; Wavelength, Giving Rise to Observedμ Absorption Band______________________________________ 2.95 free OH or bounded OH stretching of polymers, (free) NH stretching3.4 and 3.5 C--H stretching (CH.sub.3 or CH.sub.2)4.3 P--H stretching ?5.3 ?6.0 absorbed water and C = 0 stretching6.05 and 6.45 amide bands (NH)6.2 COO.sup.--carboxylate ions stretching7.15 and 8.1 acetyl group8.7 CHOH stretching9.3 OH bending9.5 C--OH stretching10.9 and 11.3 C--H stretching______________________________________
Many different preparations of emulsifying agents were prepared for making comparisons in their elemental analysis. Crude polymer is that precipitated directly from broth with either alcohol or acetone. After precipitation the polymer was chloroform extracted, chloroform-methanol extracted, dialyzed using distilled water and an XM100 membrane (mol wt<100,000). For each preparation the percentage nitrogen, corresponding percentage protein and percentage sugar was determined. The resulting data are summarized in Table 3.
TABLE 3______________________________________ N expressedPreparation %N* as % protein % Sugar**______________________________________Crude Polymer 4.2 26 34Chloroform extract 3.5 22 36Chloroform-methanol (2:1) 1.5 9.5 43extractDiethyl ether extract 2.4 15.5 38Dialyzed-XM100 1.3 9.0 50(>100,000 mol wt)______________________________________ *Elemental N determined by automatic analyzer **Sugar determined by colorimetric reaction with antrone reagent and expressed as glucose equivalent
An automatic carbon-hydrogen analyzer was used to analyze the most purified fraction (dialyzed-XM100), i.e. greater than 100,000 mol. wt. The carbon content was calculated to be 43.5% and the hydrogen 10.5%. Typical hexose carbohydrates contain ˜ 40% C; ˜ 6.6% H and typical proteins contain ˜ 50% C; ˜ 7% H. The highly purified polymer contained 0.015% phosphorus by the colorimetric method of Ernster. To show the presence of phosphorus the emulsifying agent had to be hydrolyzed since non-hydrolyzed material gave no reaction. Upon ashing the purified emulsifier, approximately 10% ash was obtained for dialyzed samples and approximately 1% ash for samples precipitated by alcohol.
The following tables illustrate typical optimum conditions for maximizing the production of the polymer material accompanied by corresponding cellular production.
Table 4 shows the yields obtained in shake flasks with longchain paraffinic hydrocarbons of 11 - 20 carbon atoms.
TABLE 4______________________________________Paraffinic Cellular Yield Polymer yieldhydrocarbon g/100 ml dry wt g/100 ml dry wt pH______________________________________C.sub.11 0.038 0.028 5.3C.sub.12 0.054 0.054 5.0C.sub.13 0.054 0.053 4.7C.sub.14 0.027 0.035 4.6C.sub.15 0.030 0.093 4.7C.sub.16 0.022 0.048 5.0C.sub.17 0.005 0.026 4.6C.sub.18 0.022 0.044 4.5C.sub.19 0.059 0.039 5.7C.sub.20 0.064 0.023 4.7______________________________________
These figures were obtained using a nutrient medium in which ammonium sulphate was used as a source of nitrogen and not sodium nitrate. As the ammonium is utilized the pH of the system decreases and inhibits growth. The production of polymer with ammonium sulphate is poor and sodium nitrate is preferred.
Table 5 below shows the effect of varying amounts of kerosene present in the culture medium, as a typical mixture of long chain paraffinic hydrocarbons.
TABLE 5______________________________________ cellular polymer% kerosene % kerosene dry wt dry wtvol/vol wt/wt gm/liter gm/liter______________________________________0.5 0.375 3.0 2.01.0 0.75 6.0 3.51.5 1.125 9.0 4.22.0 1.5 12.0 4.53.0 2.25 14.0 6.54.0 3.0 16.0 7.05.0 3.75 15.0 4.8______________________________________
It will be seen that a maximum was obtained at 4.0% kerosene. However in a batch fermentation an economical operating range for optimum yields is found to be between 1 and 2% by volume. Considerably more than 5% may be employed and up to 10% of paraffinic hydrocarbon, either by volume or by weight, may be added.
Table 6 below shows the effect of the addition of yeast extract to the nutrient medium. The experiments were conducted with shake flasks and an incubation period of 10 days.
TABLE 6______________________________________ cellular polymer% yeast extract dry wt dry wtwt/wt gm/liter gm/liter______________________________________0 4.0 3.00.1 9.0 5.30.2 10.0 5.60.3 11.0 6.00.4 9.7 5.70.5 9.0 5.0______________________________________
It will be seen that growth and polymer production increase enormously with the addition of yeast extract, but a peak is reached at about 3% by weight, and thereafter a decrease from the maximum is obtained.
Table 7 below shows the effect of varying the percentage of inoculum added, the inoculum used being 7 days old. A separate series of experiments showed that the inoculum should be at least 5 days old. There is a steady increase of yield with increase of inoculum.
TABLE 7______________________________________ cellular% inoculum dry wtby vol. gm/liter______________________________________1 7.53 8.65 9.57 10.010 10.8______________________________________
As indicated above, the fermentation broth, the precipitated polymer and the isolated polymer are all usable and highly effective as emulsifying agents for long chain paraffinic hydrocarbons (e.g. of carbon content greater than 10), particularly fuels such as kerosene and Bunker C fuel oil.
The experiments for determining emulsification characteristics were carried out in two stages: (1) emsulsification of kerosene and Bunker C oil in distilled water, (2) emulsification of Bunker C oil in artificial sea water at different temperatures. Each of the emulsifying products was dissolved and/or suspended, as the case may be, in distilled in water were placed in 500 ml Erlenmeyer flasks and specified dosages of either kerosene or Bunker C oil added. Agitation was supplied by placing mixtures on a New Brunswick rotary shaker at 200 ppm (˜25° C). The oil droplets from the emulsion were measured under a microscope after 24 hours. For this purpose the emulsion was stabilized in gelatin using the technique described by Katinger et al., 1970. One hundred droplets of oil from the sample were informatively measured and the droplet size distribution was statistically evaluated by using a computer program. The kerosene used in the experiment contained primarily dodecane, tridecane, tetradecane and pentadecane. The Bunker C fuel oil contained 34.2% of saturates, 38% aromatics, 18.8% polar compounds, 9% asphaltenes and 1.66% sulphur on a weight basis. Its viscosity at 15° C was 460 poises. Artificial sea water medium (McLachlan, 1959) was used.
Table 8 below shows the results of using the purified polymer as an emulsifying agent. The purified polymer in concentrations of 0.001, 0.01, 0.02 and 0.05% by weight were added to water (w/w) and used to emulsify kerosene. The kerosene levels tested were 5, 10 and 30% (v/v). Droplet size depended on whether the sample was removed from the top or bottom of the test vessel. It also was dependent upon the concentration of polymer added and the dosage of kerosene. At 0.001% concentration polymer droplet formation is restricted to the top area, whereas at 0.01% large droplets of 1-4 mm are found in the top area and small droplets of 4.17-5.3 μ are found in the bottom layer. At 0.05% polymer upper and bottom zones are lost and an homogenous emulsion is observed (3.9-5.66 μ).
TABLE 8__________________________________________________________________________ Droplet sizeEmulsifier (diameter)in Water Kerosene Top Bottom% (w/w) % (v/v) Type of Emulsion * **__________________________________________________________________________ 0.001 5, 10 A signification forpolymer and 30 emulsification in top oil layer - -0.01 5 Two emulsions were formed: 1-4 4.17 μpolymer 10 top emulsion rich on oil mm 4.25 μ 30 phase with big droplets 5.30 μ and bottom emulsion with fine droplets of oil dispersed in water phase0.02 5, 10 The same as with 0.01% + +polymer and 30 polymer in water0.05 5 A homogenous emulsion 3.91 μpolymer 10 3.99 μ 30 5.66 μ__________________________________________________________________________ * by visual observation ** arithmetic mean diameter from statistical evaluation of 100 droplets measured under microscope - no emulsification observed + droplets not measured
These same indicia are used also in Tables 9 to 11.
Tables 9 and 10 below show the emulsification of Bunker C fuel oil respectively with purified polymer and fermentation broth. The concentrations of fermentation broth tested were 0.05, 0.1, 0.5, 1.0, 2.0 and 3.0% (w/w) The levels of Bunker C oil used were 5 and 10% (v/v). At 0.01% purified polymer, the emulsification starts but oil and water separate upon standing. There is a considerable amount of Bunker C adhering to the glass surface in all test samples except at 0.05% polymer where the oil is almost completely emulsified.
At 0.05% purified polymer and at either 5 or 10% Bunker C oil the droplet size at the top of the vessel was 2.5 mm whereas sample from the bottom shows an average droplet size of 1.7μ. The fermentation broth containing polymer and cells of C. hydrocarboclastus also gives good emulsification. Addition of 1.0 and 2.0% fermentation broth to water (w/w) was equivalent in emulsification capability to .05% polymer. Under these conditions, the droplets of Bunker C oil were smaller than those observed with kerosene.
TABLE 9__________________________________________________________________________ Droplet sizeEmulsifier "Bunker C" (diameter)in Water oil top bottom% (w/w) % (v/v) Type of Emulsion * **__________________________________________________________________________0.001 5 and 10 No emulsification, heavypolymer deposit of oil on walls - -0.001 5 and 10 A signification forpolymer emulsification in bottom water layer, heavy deposit on walls - -0.02 5 and 10 Increasing emulsification,polymer still heavy deposit of oil + + on walls0.05 5 and 10 Two emulsions were formed:polymer top emulsion rich on oil phase with big droplets 2-5 mm 1.7 μ and bottom emulsion with very fine droplets of oil dispersed in water phase__________________________________________________________________________
TABLE 10__________________________________________________________________________ Droplet sizeEmulsifier "Bunker C" (diameter)in water oil top bottom% (w/w) % (v/v) Type of Emulsion * **__________________________________________________________________________0.05 and 5 and 10 No emulsification,0.1 "Bunker C" oil deposited - -ferm.broth on walls1.0 5 and 10 Good emulsification,ferm.broth top layer of emulsion + 2.1 μ contained big droplets of oil.2.0 5 and 10 Very good emulsification,ferm.broth only thin layer + 1.69 μ emulsion with big droplets of oil3.0 5 and 10 Still good emulsificationferm.broth but worse than with 1 and + + 2% - probably overdosage__________________________________________________________________________
A similar set of experiments were conducted in an artificial sea water medium and the results are shown in Table 11. Emulsification was tested at two different temperatures: 7° C and 25° C. The concentrations of polymer were 0.05 and 0.1% (w/w), the concentrations of fermentation broth were 0.5, 1.0 and 2.0% (w/w) and the concentration of cells+ polymer precipitated from fermentation broth were 0.5, 1.0 and 2.0% (w/w). The test systems contained 90 ml of aqueous polymer product and 10 ml of Bunker C oil.
TABLE 11__________________________________________________________________________ Droplet sizeEmulsifier (diameter)in sea water Temp. top bottom% (w/w) ° C Type of emulsion * **__________________________________________________________________________0.05 7 Emulsification only on top 5 mm -polymer into big droplets 25 Two types of emulsion 3-5 mm 1.77 μ0.1 7 Two types of emulsion 1-3 mm 1.55 μpolymer 25 Two types of emulsion 1-3 mm 1.68 μ0.5 ferm.broth 25 Two types of emulsion 2-3 mm 1.9 μ1.0 ferm.broth 25 Emulsification only on top 5 mm -2.0 ferm.broth 7 Two types of emulsion 1-3 mm 1.7 μ 25 Emulsification only on top 5 mm -0.5 polymer 7 Homogeneous emulsions, only + 1.8 μ+ cells 25 few big droplets of oil on + 1.87 μ top1.0 7 At 7° C the emulsification + 1.66 μ 25 was completed in 72 hrs, at + 2.16 μ 25° C in 24 hrs.2.0 7 + 1.56 μ 25 + 1.5 μ__________________________________________________________________________
In general, emulsification in sea water was not quite as good as was observed in fresh water. However, the test results are favourable. A concentration of 0.1% pure polymer gave 1-3 mm diameter droplets in the top layer and 1.55-1.68 μ droplet in the bottom layer. The degree of emulsification of Bunker C oil with fermentation broth gave droplets in the top phase of 1-5 mm and droplets in the bottom phase varying from 0-1.9 μ. Although the 2.0% fermentation broth contains > 0.05% polymer, the emulsification was not as good. Interferences can be attributed to salts in the broth, cells and other organic intermediates present. Crude polymer and cells precipitated from broth gave excellent emulsification at both 7° and 25° C.
In all instances agitation and mixing became more important as the temperature is lowered.
Although the use of these agents has only been evaluated and described in connection with specific hydrocarbon materials it will be understood by those skilled in the art that they are usable also with other materials commonly requiring emulsification such as steroids, oils and fats, specifically corn oil, soya bean oil, beef, lard, etc. They may also be used in association with other materials in applications for example such as the removal of oily stains from clothing and other fabrics.
TAXONOMY OF THE CULTURE
The culture is a Gram-positive bacterium which shows snapping division and becomes coccoid forming cystites after 48 hrs. It fits well in the family of Corynebacteriaceae and since it does not utilize cellulose, it cannot be placed in the genus Cellulomonas. It differs from the genus desciption of Corynebacterium by being strongly urease positive, catalase positive, and gelatinase negative. It is similar to Corynebacterium hydrocarboclastus (Iizuka and Komogata, 1964) in that growth is observed on glucose, lactose, xylose, as well as in other major characteristics described. Urease activity has not been reported for this microbe. This culture is also similar to Arthrobacter luteus as described by Kaneko et al. (1969). It differs by showing negative gelatin liquefaction, alkaline reaction in milk, no production of nitrite from nitrate, and no acid production from carbohydrates. Because it fits best into the genus description of Corynebacterium and differs from Arthrobacter by being urease positive and always Gram positive, it has been placed in the genus Corynebacterium. Except for urease production, which has not been reported, the culture possesses all the characteristics of Corynebacterium hydrocarboclastus.
The following Table 12 summarizes various tests that were carried out in the establishment of the taxonomy of the culture.
Viable samples of the culture have been deposited in fulfillment of the requirements of 35 U.S.C. 112 in August, 1972 in the culture collection of the University of Western Ontario, London, Ontario, Canada and have been given the reference number 409. Another deposit has been made with the Northern Utilization Research and Development Division of the Agricultural Research Service of the United States Department of Agriculture, Peoria, Illinois, and has been assigned designation NRRL-B-5631. A further deposit has been made with U.S. Army Natick Laboratories, Natick, Mass.
TABLE 12______________________________________TESTS CORYNEBACTERIUM HYDROCARBOCLASTUS______________________________________appearance gram positive bacillus - 24 hrs gram positive breeded bacillus - 70 hrs gram positive cocci - 96 hrs (on yeast glucose at 25° C)arabinase growth but fermentation negativedulcitol growth but fermentation negativeglucose growth but fermentation negativeglycerol growth but fermentation negativelactose growth but fermentation negativemaltose growth but fermentation negativemannitol growth but fermentation negativesalicin growth but fermentation negativesucrose growth but fermentation negativexylase growth but fermentation negativegelatin growth - not liquifiedmilk alkaline - no pept., no coagulationnitrate-nitrite growth - negative reactionindole growth - negative reactionurea strong reaction - 24 hrsoxidation - growth - no reactionfermentationreaction (D-F)motility negativeoxidase negativecatalase positiveodor urea medium - ammonium yeast glucose - sweet gelatin -putridH.sub.2 S negativegrowth on varied from no growth to slight growthMacCankeymediumPellicle item pectile on all brothsacid fast stain negativestarch utilization negative - 48 hrs. Negative after five days incubation.capsule present______________________________________
The polymer fraction of the Corynebacterium hydrocarboclastus reaction product behaves as a typical polyelectrolyte and the viscosity of the polymer solution decreases sharply upon addition of salts, as is illustrated by the following table 13 showing the effect of adding two different salts, sodium and calcium chloride thereto.
TABLE 13______________________________________ Viscosity [cp] Viscosity [cp] of solution of of solution ofNaCl 0.5% (w/w) CaCl.sub.2 0.5% (w/w)[g/100 ml] polymer [g/100 ml] polymer______________________________________0 110 0 1101 12 1 135 9 5 1010 9 10 1115 8 15 11.520 8 20 12______________________________________
The emulsification by the polymer fraction of Corynebacterium hydrocarboclastus is effected by the pH of the solution and an acidic pH enhances the emulsification. For example kerosene was emulsified after 1/2 hour of agitation into a homogeneous emulsion at pH 3, into nonhomogeneous emulsions at pH 5, 7 and 9 and into an unstable emulsion at pH 11 at the concentration of 0.05% polymer (w/w). A mixture of "kerosene: Bunker C fuel oil" (1:9) was emulsified into homogeneous emulsions at pH 3, 5, 7, into a nonhomogeneous emulsion at pH and no emulsion was formed at pH 11, also at the concentration 0.05% polymer (w/w).
The interfacial tension between polymer solution and oil was effected in a similar manner in comparison with a control (water and oil). The results are summarized in Table 14 below.
TABLE 14__________________________________________________________________________ interfacial tensions__________________________________________________________________________ 0.05% water/oil pol.sol/oilpH oil or mixture of oils γ.sub.w/o [dyn/cm] γ.sub.p.s./o [dyn/cm] γ.sub.w/o-γ.sub.p.s/o__________________________________________________________________________pH 3 kerosene 35.6 28.8 6.8kerosene: bunker C oil (9:1) 22.8 14.65 8.15kerosene: bunker C oil (1:1) 24.8 14.65 9.6kerosene: bunker C oil (1:1) -- 14.5 (NaCl sol.) --pH 7 kerosene 39.9 38.1 1.8kerosene: bunker C oil (9:1) 22.8 20.3 2.5kerosene: bunker C oil (1:1) 24.8 22.8 2.0kerosene: bunker C oil (1:1) -- 22.7 (NaCl sol.) -- pH 10kerosene 38.2 38.8 0.6kerosene: bunker C oil (9:1) 20.3 19.85 0.45kerosene: bunker C oil (1:1) 22.8 22.1 0.7kerosene: bunker C oil (1:1) -- 22.1 (NaCl sol.) --__________________________________________________________________________
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An emulsifying agent of microbiological origin is produced by an aerobic aqueous fermentation process employing Corynebacterium hydrocarboclastus UWO 409 as the fermentation agent and paraffinic hydrocarbon substrate. An emulsifying agent product consists essentially of an extracellular polymer product of a fermentation process, the polymer comprising a polysaccharide component including galactose, glucose and mannose in ratio about 1:2.65:1.96 and a bound protein component.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the disposal of the waste of house pets. More specifically, the invention is an environmentally sound solution to the problem of canine waste disposal.
2. Background of the Invention
The problem of properly disposing of dog waste is as universal as is the widespread affection for dogs as pets. In the United States, it is approximated that 38% of households have a dog. This translates into a canine population of 62 million. The popularity of dogs as pets and service animals is world-wide. As found on the website, www.dog-diaper.com, The New York Times (Nov. 1, 1995) reported that canine laws around the world impose fines that try to effectively control an estimated 25 tons of canine waste produced by 250,000 dogs. It also reported that an average of 650 people a year end up hospitalized after slipping on dog waste uncollected on Paris sidewalks.
A measure of the pet waste disposal problem in urban centers is also reflected in many current U.S. canine laws, sometimes called “pooper scooper” laws, both in the U.S. and abroad. These statutes impose considerable fines upon dog owners who do not pick up after their dogs.
Various methods have been advocated for the disposal of animal waste from canine house pets. Present methods of controlling dog waste have been described in, for example, in U.S. Pat. No. 6,273,481 to Columbo et al. This art involves a kit whose components enable the dog's human walker to pick up the solid waste and dispose of it in a bag. Many dog walkers follow a similar routine using miscellaneous bags as the pickup and disposal means. Users of this and similar practices are often inconvenienced and embarrassed to pick up the waste by hand, using papers, plastic bags or cumbersome pooper scoopers in order to comply with the law.
Other art, including U.S. Pat. No. 6,471,267 to Asazuma involves ensnaring and collecting dog waste describes waste capture that minimizes a person's exposure to the waste. The waste still needs to be deposited somewhere for disposal. There are numerous patents and devices marketed as dog diapers, one of which is U.S. Pat. No. 5,234,421 to Lowman. This particular patent addresses the special needs of incontinent dogs but there are other patented and non-patented dog diapers that eliminate the need for human pick-up of the waste. The diapers are strategically placed on the dog and offer the cleanest way to deal with dog waste both outdoors and indoors, by preventing dog waste from ever being deposited on any floor or outdoor surface. A dog diaper product frees dog owners from having to pick-up waste but the full diaper still needs disposal. Putting a diaper on the dog before use and removing it after use to dispose of it in a garbage can avoids direct contact with the waste, as occurs when the waste is picked up by hand.
Several inventors, including Igual De Valles in U.S. Pat. No. 6,263,834, Janzen et al in U.S. Pat. No. 6,453,844, and Leibowitz in U.S. Pat. No. 5,494,001 have developed dog toilet-type devices which use water in some form to wash the waste away. Further toilet-like dog waste disposal is seen in U.S. Pat. No. 6,386,605 wherein Kaplan uses a strategically placed paper towel to collect dog waste which is then flushed down a household toilet. Practical success of the methods and devices are unknown.
What is known, however, is that disposal of dog waste is a growing environmental problem. Animal waste poses health hazards in city streets, parks and other public places when uncollected. Furthermore, retrieval of waste in a variety of bags for disposal in garbage cans and/or dumpsters is quite an environmental burden. Adding to the environmental insult is the fact that the unwrapped animal waste itself is very recyclable. When wrapped in a plastic bag and thrown in household trash that is usually sent to land fills, the potentially recyclable waste becomes an environmental burden.
Accordingly, it is an object of the present invention to provide a system that allows for an environmentally friendly disposal of solid pet waste into a household or municipal sewer. The animal waste may be scooped with a shovel or similar device negating the necessity and expense for dog diapers, disposal bags, and the like. The waste is then washed into the household or municipal sewer by pouring a quantity of water into a receiver and subsequently, into the sewer.
A further object of this invention is to provide a covered cylindrical plastic receiver which is easily installed in a home by connecting to the home's sewer cleanout or directly into the sewer line. In this manner, when the dog waste is found in a fenced backyard, a home owner/dog owner can easily use a shovel to deposit the waste in the receiver and a household bucket to pour water in the receiver to “flush” the waste into the sewer. Besides being environmentally friendly, there is no need for special tools or scoopers.
A still further object of this invention is to provide a version of the system for use in public parks and the like. This would be larger and constructed of stainless steel or other metal, and comply with the statutes of the municipality in which it is located.
Further objects will be made clear in the figures and detailed description of the invention which follows.
SUMMARY OF THE INVENTION
The present invention is directed to a device for the disposal of solid animal waste into a receiver which connects, through a water trap and PVC line, to a sewer. After the waste is deposited into the receiver, it is sent into the sewer by the force a quantity of water which is poured into a receiver by a person using an ordinary household bucket.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 depicts a detailed side view of the animal waste disposal device of the invention.
FIG. 2 shows an overview of the location and placement of a typical household installation of the animal waste disposal device of the invention.
FIG. 3 shows an exploded view of the animal waste disposal device of the invention in a typical vertical installation.
FIG. 4 shows a dog, an amount of solid waste from the dog, a shovel and a bucket used to dispose of animal waste in the device, system and process of this invention.
FIG. 5 depicts a typical horizontal installation of the device of this invention in conjunction with a two-way sewer cleanout.
FIG. 5 a depicts a two-way sewer cleanout.
DEFINITIONS
In this invention, a ‘household sanitary sewer’ is defined as a system that carries waste materials from throughout a home or other building leading to a municipal sewer or a septic system.
In this invention, the term ‘septic system’ will refer to a tank for receiving waste matter to be putrefied and decomposed through bacterial action and a leach field.
In this invention the term ‘municipal sewer’ will indicate a sewer system operated by a local government or municipality. The municipal sewer system will refer to a sewer that has the ability to handle and process waste from a number of homes, businesses or other buildings.
In this invention, a ‘one-way sewer cleanout’ defines an opening in a drainage line that provides one-way access to the inside of a household sanitary sewer. A one way sewer cleanout is generally installed to provide access to remove and unblock obstructions in the household sanitary sewer line towards the municipal sewer or septic system.
In this invention, a ‘two-way sewer cleanout’ defines an opening in a drainage line that provides two-way access to the inside of the household sanitary sewer, allowing clearing of obstructions in the sewer line which may be located either in a direction towards the municipal sewer/septic system or towards the house.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to the figures, FIG. 1 shows the animal waste disposal device of this invention. FIG. 2 shows the device installed on the outside of a residential home or other building. The device includes a cylindrical receiver 1 , which is adjacent to the household sanitary sewer 17 of a building, such as a home 15 . It is largely underground, as indicated by the ground level indicator 2 .
Connected to and below the receiver 1 is a molded basin 3 with a water trap 5 leading to a PVC line to the household sanitary sewer 17 . FIG. 2 shows a typical installation of the animal waste disposal device of this invention on the premises of a private residential home 15 . The position of the home's foundation 16 in relation to the household sanitary sewer 17 and municipal sewer 14 are shown.
FIG. 3 depicts an enlarged, more detailed view of the animal waste disposal device of this invention installed in a vertical fashion. Illustrated therein are the receiver 1 , the basin 3 , the water trap 5 which leads to the PVC pipe 12 . The wye fitting 18 is shown installed vertically between the one way sewer cleanout fitting 27 and the sewer cleanout cap 19 .
The majority of residential homes in the United States have one-way sewer cleanout fittings 27 , as described above. In the case of homes that have two-way sewer cleanouts 25 , as seen in FIG. 5, each end of the two-way cleanout 25 points to both the home 15 and the municipal sewer 14 . The overview of FIG. 2, showing an embodiment of the installed device of this invention, a home 15 , the household sanitary sewer 17 , and the municipal sewer 14 depicts a typical layout of these entities.
If a home 15 has a two-way sewer cleanout 25 , installation of the animal waste disposal device of this invention is installed with the wye fitting 18 installed horizontally. In this manner, the installer exposes a small section of the household sanitary sewer line 17 and installs a PVC wye 18 in its place.
To install the animal waste disposal device of this invention in a home with a one-way sewer cleanout fitting 27 installation of the device will be vertically. The procedure for its installation, either horizontally or vertically, is relatively easy and without the need for special tools or the services of a contractor. The tools needed for the vertical installation include items such as a shovel 23 and tools such as a hand saw, tape measure, level, glue used with PVC, paper towels, a knife and/or sandpaper, and a flashlight (not shown). For buildings with a two-way sewer cleanout, a horizontal installation is required. For a horizontal installation, additional supplies include two 3″ no-hub rubber plumbing (Femco) couplings 26 , a screw driver and/or nut driver, and gloves (not shown).
First Preferred Embodiment
Vertical Installation to a One-way Sewer Cleanout
To begin a vertical installation of the device of this invention, FIG. 3 shows the sewer cleanout cap 19 of the sewer cleanout pipe 20 which is removed and set aside. The installer must look into the cleanout pipe 20 with a flashlight (not shown) to determine if the cleanout fitting at the bottom of the cleanout pipe 20 is a one-way 27 fitting (vertical installation needed) or two-way 25 fitting (horizontal installation needed).
The installer must determine where s/he wants to position the basin 3 of the animal waste disposal device. This will be important once the animal waste disposal device and system is installed since the basin 3 will be used for depositing animal waste 22 for disposal. It is also an important safeguard before installation is begun to make sure that no underground utilities are located in the installation area.
With the shovel 23 or other excavating device, a hole with surface dimensions of about 16×28 inches and about 20 inches deep is made adjacent to the sewer clean out pipe 20 . After excavating the hole, all loose dirt and debris from the hole must be removed. The top of the sewer cleanout pipe 20 must now be cut and removed in order to add the wye fitting 18 to it.
The top of the sewer cleanout access pipe 20 is cut with a hand saw about 20 inches below ground level 2 . Next, any burs are removed from the cut with a knife or sand paper (not shown). Any dirt on the outside of the top of the sewer cleanout pipe 20 is removed with paper toweling. When the top of the sewer cleanout pipe 20 is clean, the PVC wye fitting 18 is glued in place. Glue is applied to the outside of the sewer cleanout pipe 20 and to the bottom of the wye fitting 18 . The wye fitting 18 is then pushed and twisted onto the sewer cleanout pipe 20 , insuring its alignment with the center of the hole. It is held in place for about 20 seconds while the PVC glue dries and cures.
Next, about 6½ inches of the bottom of the sewer cleanout pipe 20 is cut off with a saw (not shown), and burrs are removed. The sewer cleanout pipe 20 and cleanout cap 19 is now reinstalled in top of the wye fitting 18 .
In order to complete installation of the animal waste device of this invention, about 7½ inches of three inch PVC pipe 12 is cut and burrs removed. The piece is then glued into the wye fitting 18 . (All gluing described should be according to package instructions of the PVC glue used, regarding ventilation and manner of attachment.)
At this point, a small wad of paper toweling (not shown) is put in the end of the 7½ inch piece of PVC pipe 12 . Being careful not to get dirt in the PVC pipe 12 , about nine inches of dirt should be shoveled back into the original hole dug around the sewer cleanout pipe 20 . It is critical not to overfill, so that the receiver 1 will fit in place properly with respect to the other components of the animal waste disposal device of this invention.
At this point, the wad of paper toweling is removed and glue applied to the outside of the length of 3 inch PVC pipe 12 and to the inside of the 3 inch PVC connection 10 and fitted together. Before glue cures, the installer levels the receiver 1 . This will insure that the completed animal waste disposal device will function properly. The rest of the soil originally excavated is now replaced around the receiver 1 and cleanout pipe 20 . A small amount of crushed rock, bark dust or other decorative material (not shown) may be placed around the unit for both decoration and to keep mud and dirt from interfering with the operation of the animal waste disposal system of this invention.
Second Preferred Embodiment
Horizontal Installation Involving a Two-way Sewer Cleanout
To install the animal waste disposal device of this invention in a home or building with a two-way sewer cleanout 25 , as seen in FIGS. 5 and 5 a , the depth of the sewer line 17 from the ground level line 2 must be measured. To this value, twelve inches must be added to determine the horizontal distance from the sewer cleanout pipe 20 that must be excavated and exposed. Twelve inches is added to this measurement due to the geometry of the wye fitting 18 and the relative position of the PVC connector 10 to the ground level indicator 2 on the receiver 1 . For example, if the sewer line 17 is measured vertically and is found to be 18 inches from where the ground level indicator 2 would need to be for proper installation of the device, then twelve inches is added to the eighteen inch dimension, making a total of 30 inches.
In this example, thirty inches is the horizontal dimension from the cleanout pipe 20 to the point to be excavated 28 . Excavation point 28 is the center of the length of sewer pipe 17 that will be removed. (The earlier cautionary statement about underground utilities should be heeded here as well.).
After determining the area to be excavated from this measurement and calculation, a sixteen to twenty-inch section of the sewer line 17 is then exposed by digging with a shovel 23 or other excavating means. Excavation to a level that is an inch or two below the sewer line 17 is required to gain access so that the installer can easily cut sewer line 17 .
After the digging to expose the sewer line 17 is complete, the installer digs toward the home 15 to make room for the installation of the component parts of the animal waste disposal device of the present invention, including the cylindrical receiver 1 , the molded basin 3 , the lid 6 , the lid activator 7 , the hinge pin 8 , and the lid stop 9 as seen in FIG. 5 . Then, two three-inch lengths of PVC pipe 12 are cut. The pieces of PVC pipe 12 are glued to each end of the straight part of the wye fitting 18 . This is done by applying glue to the inside of the wye fitting 18 and to one end of the two three-inch lengths of PVC pipe 12 . The PVC pipe 12 is twisted and inserted into the wye fitting 18 and held firmly for about 20 seconds. The gluing is repeated for the other length of PVC pipe for attachment to the other end of the wye fitting 18 .
The installer then measures and confirms that the distance between the ends of each three-inch length of PVC pipe 12 is about 10 inches. The installer then refers to the earlier calculation of excavation point 28 and marks this point on the sewer line 17 . The installer then cuts a length of sewer line 17 , that is equal to plus ¼ inch of the length of the wye fitting 18 and the two three-inch pieces of PVC pipe 12 . It is important that this section of sewer pipe 17 that is cut out is centered on the calculated excavation point 28 .
The outside ends of the cut sewer pipe 17 should be wiped clean with a paper towel (not shown). Next, two no-hub three-inch (Fernco) couplings 26 are loosened and slid onto each exposed end of the sewer pipe 17 .
The wye fitting 18 is then inserted between the two ends of the sewer pipe 17 with the wye pointed upwards and towards the home 15 . The two no-hub three-inch (Fernco) couplings 26 are now slid onto the pieces of PVC pipe 12 that have been previously glued into the wye fitting 18 . After this is done, the two no-hub three-inch (Fernco) couplings 26 are tightened.
Another length of PVC pipe 12 is now cut to extend from the wye fitting 18 to the 3 D PVC connection 10 . When the fit is confirmed, one end of the PVC pipe 12 is glued to the 3″ PVC connection 10 . The other end of the PVC pipe 12 is glued to the 3″ PVC wye fitting 18 .
When this is complete, the area around the installed animal waste disposal device, the excavated earth is replaced around the outer structure of the device. Care must be taken that the receiver 1 stays level and that no pipes or fittings are strained. As in the vertical installation described, a small amount of crushed rock and/or bark may be employed here for decoration.
Illustration of the Process of Using of the Animal Waste Disposal System of the Present Invention
To use the animal waste disposal system of the invention, a dog 21 will excrete waste 22 . The dog's owner will be able to use the blade 23 a of a shovel 23 to lift the waste 22 and walk it over to the animal waste disposal system. The owner (not shown) will depress a lid activator 7 with his foot which will lift the lid 6 of the disposal device.
Once the lid 6 is open, the owner can deposit the waste 22 and deposit it into the device's basin 3 . Once this is done, the owner can fill a bucket 24 with a quantity of water from any outside spigot (not shown) that is close to the device and deposit from about one to three gallons of water into the basin 3 . The dog's owner has now cleanly, safely, and inexpensively disposed of the waste 22 without the need for dog diapers, pooper scoopers or any other accessories. The waste 22 is now processed along with that of the rest of the household sewage.
If the animal waste disposal system of this invention is installed and used in a public area, the procedure will be the similar, but on a larger scale. The municipality that supervises the public area (park, public dog walk area, and the like) will be able to set rules and regulations as they see fit These rules can include procedures designed to collect and flush the waste and any limits on quantities and sizes of pets accommodated. The ability of the municipality to process sewage will determine (and perhaps limit) the amount of public usage of he system.
Scope of the Invention
The above presents a description of the best mode contemplated of carrying out the present invention, and of the manner and process of making and using it, in such full, clear, concise, and exact terms as to enable any person skilled in the art to which it pertains to make and use this invention. This invention is, however, susceptible to modifications and alternate constructions from that discussed above which are fully equivalent. Consequently, it is not the intention to limit this invention to the particular embodiments disclosed. On the contrary, the intention is to cover all modifications and alternate constructions coming within the spirit and scope of the invention as generally expressed by the following claims, which particularly point out and distinctly claim the subject matter of the invention.
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The current invention relates to an environmentally friendly and inexpensive way to dispose of solid animal waste that is installed in conjunction with a household sanitary sewer. The system includes a basin covered with a lid that is installed near a building's sewer cleanout. A wye filling is added to the cleanout so that waste that is deposited into the basin is washed into the household sanitary sewer by pouring a bucket of water in the basin after the waste is deposited to carry it into the household sanitary sewer.
The invention provides a solution to the need for the safe and clean disposal of dog solid waste without the need for any sort of scoopers, diapers or bagging devices.
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STATEMENT OF GOVERNMENT RIGHTS
The United States Government has rights in this invention pursuant to Contract Number DE-AC09-96-SR18500 between the U.S. Department of Energy and Westinghouse Savannah River Company
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to improved methods for the long-term treatment of wastewater and contaminated groundwater, especially contaminated groundwater from persistent sources, using self-regulating bacterial treatment requiring minimal maintenance.
2. Background and Prior Art
Persistent contamination of wastewater and groundwater presents an ongoing problem because any treatment method must be established and maintained for extended time-periods when compared to sites no longer producing contaminants. Abandoned mines leak acids and acid soluble minerals continuously and effective closure is cost prohibitive. Coal yards/piles at operating coal fired power plants are a significant point source for contamination and the leakage is expected to be continuous until the power plant is closed. Active pump and treat technologies require resources such as power, treatment chemicals and personnel. These costs cannot be incorporated into product pricing under any economically sound scenario.
On site and in situ bioremediation schemes offer promise of lower cost and acceptable thoroughness but systems attempted to date have not found general acceptance. Examples of such treatment methods may be found in U.S. Pat. No. 5,076,927 to Hunter; U.S. Pat. No. 5,514,279 to Blowes, U.S. Pat. No. 5,772,887 to Noah et al.; U.S. Pat. No. 5,833,855 to Saunders; U.S. Pat. No. 5,922,204 to Hunter; and U.S. Pat. No. 6,398,960 to Borden. A survey of technologies particularly adapted to mine drainage is Handbook of Technologies for Avoidance and Remediation of Acid Mine Drainage , Skousen et al. eds., National Mine Land Reclamation Ctr., Morgantown, 1988.
The technologies proposed in the above-identified references are difficult to regulate on an on-going basis due to outflow seepage, plugging, and difficulty in regulating the operational rate of the treatment method. The need exists, therefore, for a treatment system which is stable, effective for the contaminants to be treated, does not require frequent attention, easily replenished and easily cleaned of solid debris. It is particularly desirable that the system has little or no power requirement and that once established will be operable for multiple years if not indefinitely.
BRIEF SUMMARY OF THE INVENTION
We have developed a bioremediation method and apparatus which is specific for the contaminants to be treated, is long lasting, requires infrequent attention, is stable and requires irregular addition of inexpensive, readily available, easy to handle biochemical energy sources.
A treatment zone is established by creating a void area in or above ground, depending on water source. The zone has sides, top and bottom, an inlet for water to be treated, an outlet for treated water, and at least one inlet by which a nutritive substrate can be added. Using endogenous bacteria from the contaminated site, selected bacteria from a similar site, or organisms cultured in a laboratory, a community of naturally selected bacteria is established within the treatment zone.
The bacteria are a mixture of species from the same or related genera and are facultative or obligate anaerobes selected in situ or ex situ for reaction/reduction of the contaminants present. The bacteria have in common that they require electron donors in their culture media. Of this consortium, the bacteria responsible for contaminant removal have in common the requirement of a terminal electron acceptor (TEA) that allows for respiratory growth under anaerobic conditions. TEAs will be redox active inorganic oxides or chlorinated organics. Contaminant removal will occur by either direct reduction, when that particular contaminant is chemically reduced by bacteria or by indirect reduction when a reactive end-product of anaerobic respiration [i.e. H 2 S or Fe(II)] reacts chemically with a contaminant to produce an insoluble mineral.
The electron donor/nutrient for the bacteria are biodegradable oils and waxes. The biodegradable oils are relatively inexpensive. High purity is not required. The oils float as a separate phase on the water being treated and degrade slowly to provide a steady nutritional source for the bacteria.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic of a generic treatment system.
FIG. 2 is a schematic of a treatment system with containment devices.
FIG. 3 is a schematic of a treatment system including biological support media.
FIG. 4 is a schematic of the system of FIG. 3 modified to include a previous separator layer.
FIG. 5 is a schematic of an alternative treatment system with a particulate removal system beneath the treatment zone.
DETAILED DESCRIPTION OF THE INVENTION
The invention is a method of bioremediation characterized by treatment means that prevents migration of bacteria and nutrients away from the treatment zone, concentrates precipitated and accumulated solids in a collection zone to limit clogging of the system and which is stable over extended periods of time.
It has been reported in the patents listed supra and in other documents that indigenous bacteria, typically of multiple species and sometimes of different genera become selected in the presence of contaminants and become effective treatment agents for a time. Maintaining viable in situ treatment zones is difficult because different flow rates on the surface and in the vadose zone induce migration in an uncontained treatment zone. Treatment zones that have restrained movement tend to become plugged with solids including precipitates of some metals and decomposed organic matter including cellular debris.
Anaerobic bacteria are useful in bioreactors of this type, and require a source of nutrients, especially electron donors. Lactates, organic waste products such as mulch, pine needles and decaying leaves have been reported as sources (Borden et al., U.S. Pat. No. 6,398,960 reports injection with emulsified vegetable oils, molasses or leachate into the ground).
Sulfate reducing bacteria (SRB) are obligate anaerobes which survive exposure to oxygen, presumably in a resting state, until a suitable environment is established by a mixed microbial community. SRB's reduce sulfate to sulfide, generating H 2 S. The sulfates are electron acceptors and SRB's require electron donors to function. SRB's function well at pH values greater than 5.5, 6.6 being reported optimal for some species. We have found isolated activity in solutions as acidic as pH2. [Tuttle, J. H., P. R. Dugan and C. I. Randles. 1969. Microbial Sulfate Reduction and its Potential Utility as an Acid Mine Water Pollution Abatement Procedure. Applied Microbiology. 17:297–302.] SRB-mediated sulfate reduction is expressed by the simplified equation:
2CH 3 CHOH COO − +3 SO 4 −2 +2H + 6 HCO 3 − +3H 2 S
In the presence of H 2 S, divalent metals are precipitated as their sulfides. Production of carbonate gradually raises the pH to preferred levels even though protons are generated in the precipitation reactions
In addition to an electron donor such as a fatty acid, trace amounts of phosphate and nitrogen are required. The sulfate reducers may be considered as indirect reducers because they produce H2S which in turn precipitates a metal or actinide abiotically as the sulfide.
A second group of bacteria are indirectly acting because by raising pH or increasing the CO2 concentration they cause precipitation through changing the solubility of the metal in the less favorable conditions (e.g., precipitate as the hydroxide or carbonate). Al, which is toxic to many bacterial species, is removed in this way, as are chromates.
We have found that a stable nutrient/electron donor source is a vegetable oil floated upon the layer of contaminated water. Unlike needles and leaves, no solids are introduced which can plug the outlet from the treatment zone. Unlike emulsified oils and water soluble nutrients, the floated oil does not flow out of the zone with the treated water.
The nutrient oils useful in this invention are not particularly limited. Any natural organic compound with negligible water solubility (e.g. <5%) and a specific gravity less than 0.99 is suitable. Preferred are “vegetable oils,” including canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, palm kernel oil, peanut oil, safflower oil, soybean oil or sunflower oil, oils of animal origin such as beef oil and cod-liver oil and waxes such as tallow, candelilla oil, carnawba wax, beeswax, cotton wax, palm tree wax. Purity is not critical and mixtures are suitable. All of the oils and waxes can be saponified by various indigenous organisms including some SRB's to produce fatty acids of decreasing chain lengths when metabolized by a variety of indigenous organisms, typically fermentative bacteria. The shorter chain fatty acids are the requisite electron donors to support the SRB's. Mineral oil may be used but is less preferred.
The treatment zone may be above or below ground, depending on the hydrology and topography of the area. Above ground treatment zones and below ground zones may be formed from water barrier materials such as concrete, FRP, metal, or HDPE. Excavations may have stabilized sides and be lined with butyl rubber. Above ground or partially buried treatment zones require a roof, preferably a floating roof. Below ground location is preferred in colder climates.
Water may be directed to an inlet into the treatment zone by a funnel and gate system, GeoSiphon™ or GeoFlow™, flumes, sluice boxes, channels, troagls, perforated or solid pipes, bergs and trenches.
Within the treatment zone microbial growth rates are controlled by the concentration of limiting nutrients (i.e. carbon sources). Nutrients are converted to microbial biomass and also provide energy for microbes to transform contaminants. In flow-through systems growth is a function of the rate of nutrient addition. Another factor that controls nutrient concentration is the flow rate of water through the system. In this case the dilution factor (D) is proportional to the flow rate (F) divided by the aqueous volume (V) in a system:
D=F/V (1)
For slow moving water D is slightly greater than 0. As the flow increases in a system, D approaches 1. Essentially D is a measure of mean residence time of nutrients in a bioreactor or a subsurface reactive zone.
In environmental systems the flow rate at any given site can vary due to changes in water input into the system. In order for microbial growth to occur at near optimal rates, the nutrient concentration, (s), must match D. In addition, the rate of the depletion of nutrients is a function of microbial growth rate and microbial density. So for microbial growth to continue at optimum rates, nutrient concentrations must be controlled relative to these variables.
When growth rates are balanced between flow and nutrient conditions, steady state growth is reached. This can be explained as follows:
The rate of change of growth limiting substrate (s) is equal to the input rate of fresh substrate (DS R ), minus the rate of substrate removal out of the system (D s ), minus the rate of substrate removal by microbes (μx/Y). Where μ is the microbial growth rate, x is microbial mass and Y is the microbial energy required to maintain physiological functions of the cell, excluding growth. This can be written as follows:
ds/dt =( DS R −D s )−(μ x/Y ) (2)
Steady state conditions are established when growth, dilution rate and nutrient additions are balanced, in other words when ds/dt=0.
At steady state conditions, when the microbial growth approaches maximum (μ max ), the system is operating very efficiently, both physiologically as well as economically from the point of view of bioremediation. In order to maintain near optimum conditions nutrient concentrations need to vary as changes in microbial concentration, flow rate, and changes in microbial growth rates due to their physiological state (i.e. temperature changes, stage of growth, or potential contact by inhibitory compounds). Microbial activity under specific conditions can be defined with the term K s , which is a measure of the nutrient requirement to achieve one half of μ max . Therefore, steady state conditions can be written as:
D =(μ max. ŝ )/( K s +ŝ ) (3)
and as:
ŝ =( DK s )/(μ max −D ) (4)
where ŝ is the steady state growth-limiting substrate concentration and it is assumed that ŝ>K s . Thus steady state can be determined and maintained when the above conditions are known. For use in remote settings in the environment it is impractical to monitor all necessary variables to achieve steady state microbial growth and performance.
The invention described here uses the low solubility of non-aqueous biodegradable organics to regulate nutrient concentrations to microbes as variables change over time. As the organics are utilized for microbial growth under varying conditions and ŝ changes (equations 3 and 4), the amount of organics that dissolve from the non-aqueous bulk phase will also vary as a function of ŝ to approach μ max (equation 4). Because the organics described here are low in solubility and lighter than water, they will remain in place longer without removal from the system as a function of flow rate. Thus nutrient loss in the system is not affected by D (equation 1). Consequently equation 4 can be simplified to:
ŝ =( K s )/μ max ) (5)
In addition, as organics are utilized from the aqueous phase for microbial growth, the organic concentration (ŝ) in contact with microbes for growth will remain a function of Ks for any given growth condition (i.e. temperature). Growth rates are expected to be maintained at near steady state for any set of growth conditions due to the self-regulation of organics into the system, which is a function of dissolution of organics from the non-aqueous phase into the aqueous phase. This is because even though the organics are minimally soluble, as the dissolved organics are utilized by microbes, more organics dissolve into the aqueous phase and the rate of solubility, not the degree of solubility maintains constant nutrient concentrations in the system. Nutrient utilization varies from the non-aqueous phase as a function of microbial activity in the subsurface. Therefore, this technology employs a self-regulating, non-aqueous organic nutrient source in the bulk phase as a nutrient reservoir.
FIG. 1 is a generic treatment system design. Treatment zone 1 may be an excavation, a tank or any volume into which contaminated water can be introduced and withdrawn. A bottom 3 provides a surface for precipitated metals to accumulate. Sides 5 and 7 (there must be complete containment in the form of any geometric figures) are penetrated by an inlet 9 for the introduction of water to be treated and an outlet 11 to discharge treated water. A top 13 encloses the zone and serves to exclude oxygen and other gasses, liquids and solids. If underground, top 13 also serves as thermal insulation. Penetrating the top 13 are a substrate addition port 15 through which nutrients such a biodegradable oil may be added and an optional opening 17 for removal of precipitated material from the bottom of the treatment zone.
FIG. 2 shows a modification of the system on FIG. 1 wherein baffles 21 and 23 create an anteroom 25 and a recessional room 27 . The baffles quiet the treatment zone 1 , retarding eddy currents and mixing.
FIG. 3 illustrates the use of biological support media 31 . Biological support media are very high surface area, inert, porous materials to which bacteria attach. Such media facilitate the formation of biofilms of organisms and allow localized growth of facultative anaerobes in the early stages of the establishment of the treatment zone. The total organism count becomes higher and flushing of organisms is diminished because the bacteria are attached to the media as a lawn. Removal of precipitate is facilitated by the use of a snorkel pipe 33 which may be used to pump the bottom of the zone through a diaphragm sludge pump.
Separation of precipitate may be facilitated as shown in FIG. 4 where a previous separator 35 such as a screen may be used to isolate biological support media from the precipitate zone 3 .
FIG. 5 illustrates an alternative approach to precipitate removal, especially useful in above-ground and shallow placement. The bottom floor 37 of precipitate zone 3 is tilted toward an end or the middle and precipitate removal port 37 draws from the low point of the floor 37 .
The system of this invention has multiple advantages. Selection of indigenous organisms in the treatment area provides a low cost, constantly replenishing source of the desired bacteria. Location of the treatment zone downstream of the contamination source, together with suitable directing means, eliminates any need for pumping. Use of a biodegradable oil or wax mixture provides a continuous release of nutrients at a rate not controlled by any external device. The oil or wax is present as a separate phase and depletion is caused only by utilization, not by flushing as would occur with an emulsion. Solids in the system are limited to solids in the inputted water and precipitates formed in situ. Replenishment requires pumping more oil/wax into the additional port. Precipitate removal is by pump. A few visits to the site in the course of a year is the only maintenance required.
The proper operation of the system according to this invention requires proper analysis of the contaminants to be treated and the available on-site chemical and biological assets.
Firstly, water or soil (in many cases a mixed wet soil sample) is collected from the area to be treated. Typical analyses of the samples would include: 1) concentration of total suspended solids (TSS) and total dissolved solids (TDS); 2) temperature at the collection point and estimates of annual temperature swings in an average year; 3) specific conductivity; 4) current pH and annual fluctuations; 5) estimated annual minimum and maximum flow rates; 6) type and quantity of contaminants including a) heavy metals; b) metalloids; c) lanthanides and actinides; d) nitrates; e) nitrites, and f) chlorinated organics. O 2 content should be determined to ensure anaerobic conditions
Next, an analysis should be made of the type and quantity of redox active oxides present which could serve as TEA's for growth and respiration for bacterial populations. Included would be: a) SO 4 −2 ; b) NO 3 − ; c) NO 2 − ; d) O 2 , e) Mn(IV); f) Cr(VI); g) U (VI); h) Fe(III) and, i) chlorinated organics.
Another sampling should be made for mixed bacterial populations capable of performing desired biochemical reactions, including partially degrading selected carbon sources for use by anaerobic respiring bacteria which can utilize available, or provide carbon sources or their breakdown products, for anaerobic respiration. Bacterial population should be screened for ability to utilize contaminants and available inorganic oxides as TEA's including a) SO 4 reducers; b) NO 3 reducers; c) NO 2 reducers; d) O 2 reducers; e) Mn(IV) reducers; f) Cr(VI) reducers; g) U (VI) reducers; h) Fe(III) reducers; and, i) reducers of chlorinated organics.
It is important to determine the dominant reaction and thermodynamic rates when multiple TAE's are present and whether SRB's are directly or indirectly acting. It is advised strongly that the growth rates of mixed populations of organisms be evaluated and the final steady state growth rate including the presence of physiological inhibitors such as Ni, Al and Sn and process inhibitors including O 2 , NO 3 , Fe (III) and Mn (IV). When inhibitors are present it should be determined whether natural selection will cause an inhibitor resistant population to emerge or whether some type of scrubbing must be initiated to suppress the concentration of inhibitors (pre-treatment).
Once the conditions at the site have been determined, the operational parameters must be decided. Organic selection will consist of non-aqueous organics with a density <0.99 and consist of compounds from the list of biodegradable oils. Preferred are “edible oils” including canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, palm kernel oil, peanut oil, safflower oil, soybean oil or sunflower oil, oils of animal origin such as beef oil and cod-liver oil and waxes such as tallow, canella oil, carnauba wax, beeswax, cotton wax, and palm tree wax. Purity is not critical and mixtures are suitable. All of the oils and waxes can be saponified (biodegradable) by various indigenous organisms to produce fatty acids of decreasing chain lengths when metabolized by a variety of indigenous organisms. The shorter chain fatty acids are the requisite electron donors to support the SRB's.
Selection (based on need) of inorganic micro nutrients, such as, Fe, W, Mo, Ni, S, K, P, N, etc, to be supplied at final concentrations of low ppm levels. The final determination of organic and inorganic nutrients will be based on;
a. assessed need; b. desired biochemical reaction rates; c. local availability (especially shipping rates), and d, costs.
The final selection of bioreactor dimensions (especially volume) will be determined based on required residence time for contaminant removal to be complete and will include:
a. flow rate of contaminant stream; b. rate of bacterial growth and contaminant removal; c. contaminant precipitation rates; d. volume of estimated solids accumulation.
Included in the determination of bioreactor of configuration will be based on;
a. local geography and topography; b. desired location, position and size of an inlet; c. desired location, position and size of an outlet; d. optional compartment upstream of contaminant reaction zone for inhibitor (i.e. oxygen) depletion;
e. optional compartment downstream of the contaminant mixing zone for BOD removal;
f. material-substantially chemically inert, low cost, (locally available, if possible)
In addition to mine and coal pile runoff, the treatment system according to this invention may be applied to the remediation of other contaminants. Halogenated hydrocarbons have been treated by Burkholderia sp. (U.S. Pat. No. 6,613,558) and Pseudomonas sp. (U.S. Pat. No. 5,998,198). Cr(VI) has been bioremediated with conditioned endogenous anaerobes (U.S. Pat. No. 5,681,739). Nitrates are a problem in well water and are treatable by nitrate reducing bacteria. As a general rule, the system of this invention is applicable to any bioremediation process wherein a two phase system can be established with a nutrient source in an immiscible phase with the contaminated water.
INDUSTRIAL UTILITY
The contaminated water treatment system according to this invention is applicable to the resolution of waste-water from coal and other mines, coal yards, runoff from chemical operations, and any other semi-permanent or permanent point source.
The invention has been described in terms of preferred embodiments. Additions and modifications apparent to those with skill in the art are included in the spirit and scope of the invention.
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A bioremediation system using inorganic oxide-reducing microbial consortia for the treatment of, inter alia coal mine and coal yard runoff uses a containment vessel for contaminated water and a second, floating phase for nutrients. Biodegradable oils are preferred nutrients.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. provisional patent application serial no. 60/636,348 filed Dec. 15, 2004, and entitled “Retractable Delineator”which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] There is a need for a retractable traffic control device suitable for use in tollways, parking garages, road diversion, lane closures, parking ramp control, or the like that is durable, resistant to the elements and easy to install.
SUMMARY OF THE INVENTION
[0003] The present invention meets the above-described need by providing an automatic retractable delineator with a housing containing a reciprocating delineator post that reciprocates through an opening in the top surface of the housing. A raising and lowering mechanism is disposed inside the housing and is mechanically coupled to the post. The housing defines an inside cavity that is provided with positive pressure to create a pressure differential between the cavity and the atmosphere. As a result, the housing is substantially protected from the elements as the pressure differential prevents foreign objects and moisture such as dirt, salt, ice, snow or the like from entering the cavity.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] The invention is illustrated in the drawings in which like reference characters designated the same or similar parts throughout the figures of which:
[0005] FIG. 1 is a side elevation view of a retractable delineator in a fully retracted position;
[0006] FIG. 2 is a side elevation view of a retractable delineator in a fully extended position and mounted in typical road-type installation;
[0007] FIG. 3 is a top plan view of the top plate showing possible mounting configurations and a sealing gasket;
[0008] FIG. 4 is a perspective view of a retractable delineator post and base showing possible reflective markings; and,
[0009] FIG. 5 is a schematic diagram of a system of retractable delineators connected in series.
DETAILED DESCRIPTION OF THE INVENTION
[0010] Referring to FIGS. 1-5 generally, and initially to FIG. 1 , a retractable delineator 10 may be utilized to alter the flow of vehicular traffic. The retractable delineator 10 has a housing 13 which is formed as an elongate hollow structure constructed of materials suitable for outdoor installation. The housing 13 is covered by a top plate 16 through which a post 19 may be raised or lowered in order to affect or control traffic conditions. The top plate 16 has an opening associated with it such that the post 19 can extend through the opening into a space above the housing 13 . Extending downward from the top plate 16 , a hollow stub 17 may be positioned around the opening to provide for stabilizing the post 19 . The stub 17 also provides for isolation of the mechanism inside the housing 13 to prevent damage to the mechanism from occurring if the post 19 is struck by a vehicle. When the post 19 is fully extended through the opening, a base 22 is surrounded by the stub 17 . The post 19 is connected to the base 22 which is mounted upon a bracket 25 . The post 19 will break away from the base 22 upon impact and the stub will prevent the base 22 from moving or transmitting force to the remainder of the mechanism. The bracket 25 is attached to a guide 28 which is able to slide vertically along a lift rail 30 , thereby raising or lowering the post 19 . The drive system may be a rodless cylinder 29 which contains the guide 28 and the lift rail 30 .
[0011] To raise the post 19 , compressed air may be passed through an air line 31 which is connected to the rodless cylinder 29 . Similarly, to lower the post 19 , compressed air may be passed through an air line 34 , thus causing the guide 28 to be lowered along the lift rail 30 . In the example shown, the drive system is a rodless pneumatic cylinder which is commercially available from Bosch Rexroth Ag of Germany. Other means for raising and lowering the post 19 such as hydraulic drives, mechanical drives, or the like would also be suitable. The various ways to accomplish the reciprocating motion of the post 19 will be evident to those of ordinary skill in the art based on this disclosure.
[0012] Turning to FIG. 2 , to install the retractable delineator 10 , a hole may be excavated in a road surface 58 and through the ground 61 below. Concrete 64 may be placed into the bottom of the hole where upon the housing 13 may be inserted and leveled such that the top plate 16 is level with the road surface 58 . Conduit 40 provides a passageway for the air line 31 and the air line 34 from the compressed air source (discussed below) to the delineator 10 . The conduit 40 may be attached to a nipple 43 thereby connecting the conduit 40 to the housing 13 . Additionally, the air line 31 and the air line 34 may be secured to a side wall of the housing 13 by means of a retaining ring 37 .
[0013] In addition to providing a pathway for running air lines 31 , 34 ; the conduit 40 provides a passageway for conditioned air to be delivered from a ring compressor 88 through the conduit 40 into the cavity 55 of the retractable delineator 10 . The conditioned air provides a positive pressure environment such that debris or water would not be able to enter through a gasket 70 ( FIG. 3 ) in the top plate 16 . By continuous delivery of air from the ring compressor 88 , the positive pressure environment inside the cavity 55 creates a pressure differential preventing the elements such as salt, dirt, ice, snow and the like from entering inside the cavity 55 . As a result, the delineator 10 is not exposed to corrosive elements or moisture which improves the durability and reliability of the unit.
[0014] After the housing 13 is positioned and leveled within the opening in the ground, concrete 64 is added to fill the remaining area around the housing 13 such that the plurality of braces 46 engage the concrete 64 to further secure the housing 13 in the hole. After the concrete 64 has cured, the top plate 16 may be removed and the rodless cylinder 29 may be installed. For ease of installation, the air line 31 and the air line 34 may be attached to rodless cylinder 29 outside the delineator 10 . Once the conduit connections are made, the rodless cylinder 29 and post 19 may then be inserted into the housing 13 using a handle 49 to slide the rodless cylinder 29 into the slide rails 52 . Once the rodless cylinder 29 is seated at the bottom of the housing 13 , the top plate 16 may be repositioned and secured to the housing 13 by means of fasteners 67 .
[0015] Turning to FIG. 3 , the top plate 16 is shown in greater detail. Fasteners 67 are disposed in openings 68 positioned around the periphery of the plate 16 . In the embodiment shown, an adaptor plate 69 is shown in the center of the figure. The adaptor plate 69 has a central opening 72 with a “clover leaf” design to receive a post 19 having a corresponding shape as shown in FIG. 4 . The adaptor plate 69 has a plurality of openings 74 disposed around its periphery for attaching plate 69 to plate 16 . As will be evident to those of ordinary skill based on this disclosure, other adaptor plates with different shapes for use with different cross-sectional shaped posts (i.e., round, square, oval, etc.) could also be used. Also, the adaptor plate 69 provides versatility for changing the post, but the top plate 16 could also be made from a single piece with an opening in the center for receiving the post 19 . The central opening 72 is bordered by a gasket 70 . Once the air reaches a certain pressure level inside the cavity 55 , it escapes to atmosphere between the post 19 and the gasket 70 . However, as discussed above, the pressure differential prevents debris or moisture from entering the delineator 10 .
[0016] Turning to FIG. 4 , the post 19 may be provided with reflective materials 76 for visibility of the post in different lighting conditions.
[0017] In one example of an embodiment of the invention, the retractable delineator 10 may be arranged as depicted in FIG. 5 where multiple retractable delineators 10 may be installed. In this particular embodiment, compressed air may be generated by a standard compressor 79 and delivered to the retractable delineators 10 via the air lines 31 and via the air lines 34 which are laid through the conduit 40 . To operate the retractable delineators, a user may select an appropriate setting on a control pad 82 which would send a signal over a wire 85 to the standard compressor 79 to provide compressed air to the appropriate air line. Additionally, conditioned air would be fed from a ring compressor 88 through the conduit 40 and into the retractable delineator 10 such that the positive pressure environment would be formed in the cavity 55 preventing water and debris from entering.
[0018] While the invention has been described in connection with certain embodiments, it is not intended to limit the scope of the invention to the particular forms set forth, but, on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.
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An automatic retractable delineator with a housing containing a reciprocating delineator post that reciprocates through an opening in the top surface of the housing. A raising and lowering mechanism is disposed inside the housing and is mechanically coupled to the post. The housing defines an inside cavity that is provided with positive pressure to create a pressure differential between the cavity and the atmosphere. As a result, the housing is substantially protected from the elements as the pressure differential prevents foreign objects and moisture such as dirt, salt, ice, snow or the like from entering the cavity.
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BACKGROUND
Light emitting diode (LED) lighting systems are becoming more prevalent as replacements for existing lighting systems. LEDs are an example of solid state lighting and have advantages over traditional lighting solutions such as incandescent and fluorescent lighting because they use less energy, are more durable, operate longer, can be combined in red-blue-green arrays that can be controlled to deliver virtually any color light, and contain no lead or mercury.
In many applications, one or more LED dies (or chips) are mounted within an LED package or on an LED module, which may make up part of a lighting unit, light bulb, or more simply a “lamp,” which may also include one or more power supplies to power the LEDs. Some units include multiple LED modules. A module or strip of a lamp includes a packaging material with metal leads (to the LED dies from outside circuits), a protective housing for the LED dies, a heat sink, or a combination of leads, housing and heat sink.
An LED lamp may be made with a form factor that allows it to replace a standard threaded incandescent bulb, or any of various types of fluorescent lamps. LED fixtures and lamps often include some type of optical elements external to the LED modules themselves. Such optical elements may allow for localized mixing of colors, collimate light, and provide the minimum beam angle possible.
In the case of an LED lamp designed to replace a tubular fixture, such as a standard fluorescent “tube” type bulb, the heat sink for the strip of LEDs inside the envelope of the bulb typically blocks light in one direction. However, if the bulb is positioned so that the heat sink is oriented up, towards the top, inside or back of the fixture and the LEDs face outward or down, such an LED lamp can be a viable replacement for a fluorescent tube.
SUMMARY
Embodiments of the present invention can provide an improved LED-based replacement lamp for a linear or “tube-type” bulb that would normally emit light in all directions around the tube. By filling the void within the lamp with an optically transmissive fluid to cool the LEDs without the use of a traditional heat sink, the light blocking effects of such a heat sink can be avoided. Thus, the LED replacement lamp can emit light in an omnidirectional pattern, making it a more natural replacement for a tube type bulb.
It should be noted that while tube-type fluorescent bulbs are given as an illustrative example of the type of lamp that could be replaced by an embodiment of the invention, any elongated type of bulb or bulb with an elongated filament or light producing element could be replaced with an LED lamp like that described herein. Other examples of bulbs that could be replaced by an embodiment of the invention include incandescent aquarium bulbs, “piano lamp” bulbs and tubular appliance bulbs.
A lamp according to example embodiments of the invention includes an enclosure with an electrical connection. The enclosure may be a tubular enclosure. An array of LED devices is placed in the enclosure and disposed to be operable to emit light when energized through the electrical connection. The array of LED devices may be a linear array. The enclosure is filled with an optically transmissive, fluid medium, which is in thermal communication with the linear array of LED devices. In at least some embodiments, the linear array of LED devices emits light in an omnidirectional pattern. This omnidirectional pattern can be achieved in any number of ways, including geometric placement of the devices in the array, the use of multiple strips of devices, or the use of LEDs with an optically transmissive substrate that allows light to radiate in all directions from the light-emitting layers of the LED. Such a substrate could be, for example, sapphire or silicon carbide.
In some embodiments, the optically transmissive fluid medium is a liquid. In some embodiments, the optically transmissive fluid medium is a gel. An index matching medium can be used as the optically transmissive fluid medium. The index matching medium can have the same refractive index as the material of the enclosure, the LED device package material or the LED substrate material. The index matching medium can have a refractive index that is arithmetically in between the indices of two of these materials. In some embodiments, the optically transmissive, fluid medium contained in the enclosure mechanically supports the array of LED devices while in thermal communication with the array of LED devices. This mechanical support allows the LEDs in the array to be connected together with little or no packaging to further enable an omnidirectional light pattern.
In some embodiments, a finished lamp suitable for use as a replacement for a fluorescent or incandescent bulb includes a power supply coupled to or connected to the linear array of LED devices to energize the devices as appropriate. A color mixing treatment can optionally be included to eliminate color tints in cases where multiple LEDs of different colors are used to produce light. Color treatments can include texturing of the tube or other parts of the lamp assembly, as well as the use of an open cell foam or a nanowire or nanowires permeated with the fluid medium. Production of white light in the omnidirectional pattern can also be achieved by using LEDs that give of light of a specific wavelength of light to energize a phosphor that coats the enclosure or is placed elsewhere within a lamp.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of a linear LED lamp according to example embodiments of the present invention.
FIG. 2 is a schematic illustration of another linear LED lamp according to example embodiments of the present invention; in this case, the embodiment includes power supply elements to allow the lamp to be powered as part of a pre-existing fixture.
FIG. 3 is a schematic illustration of another linear LED lamp according to example embodiments of the present invention.
FIG. 4 is a further schematic illustration of yet another linear LED lamp according to example embodiments of the present invention.
DETAILED DESCRIPTION
The following detailed description refers to the accompanying drawings, which illustrate specific embodiments of the invention. Other embodiments having different structures and operation do not depart from the scope of the present invention.
Embodiments of the invention are described with reference to drawings included herewith. Like reference numbers refer to like structures throughout. It should be noted that the drawings are schematic in nature. Not all parts are always shown to scale. The drawings illustrate but a few specific embodiments of the invention.
FIG. 1 is a diagram of a linear LED lamp according to example embodiments of the invention. Lamp 100 of FIG. 1 includes tubular enclosure 102 with electrical connections 104 . The tubular enclosure may be made of glass, plastic, or another suitable material. Within the lamp is a linear array of LED devices 106 , which is energized through electrical connections 104 . The linear array of LED devices can be a plurality of individual LED chips simply connected together by conductive glue, solder or welds. Different color LEDs can be mixed together to create white light. Alternatively, the LED devices can be a plurality of multi-chip devices coupled together by a wire frame structure or in some other manner. The linear array of LED devices emit light in a substantially omnidirectional or 360-degree pattern so that light is given off around the tubular structure roughly perpendicular to the envelope in all directions, in a fashion similar to that of a standard tubular bulb.
Still referring to FIG. 1 , tubular enclosure 102 is filled with an optically transmissive fluid medium 108 , such as a liquid or a gel, that has good thermal transfer properties and can provide cooling to the LED devices in the linear array. The medium is in thermal communication with the linear array of LED devices, is substantially nonconductive, and is also optionally viscous enough to support the linear array of LED devices so that the LED devices do not need to be encapsulated in electronic packaging as would be typical of LEDs mounted on circuit boards or installed in equipment panels. In at least some embodiments, the medium is an index matching medium that is characterized by a refractive index that provides for efficient light transfer with minimal reflection and refraction from the LEDs through the tubular enclosure.
As an example, if unpackaged LEDs are used, a fluid with a refractive index between that of the LED substrates and the tubular enclosure can be used. LEDs with a transparent substrate can be used so that light passes through the substrate and can be radiated from the light emitting layers of the chips in all directions. If the substrate chosen is silicon carbide, the refractive index of the substrates is approximately 2.6. If glass is used for the tubular enclosure, the glass would typically have a refractive index of approximately 1.5. Thus a fluid with a refractive index of approximately 2.0-2.1 could be used as the index matching medium. LEDs with a sapphire substrate can also be used. Since the substrate in this case would be an insulator, an ohmic contact would need to pass through the substrate of each LED. However, the refractive index of sapphire is approximately 1.7, so that in this case if glass is again used for the tubular enclosure, the fluid medium could have a refractive index of approximately 1.6. If glass lenses are used on the LED devices, the fluid could have an index of approximately 1.5, essentially matching that of both the lenses and the tubular enclosure.
It should be noted that the LEDs used with an embodiment of the invention can be completely unattached to any separate structure, and simply connected together as previously discussed. In such a case, the fluid medium services to cushion and support the linear array of LED devices to prevent damage caused by the lamp being moved about during shipping and installation, or otherwise being subjected to vibration during transport or use. However, a metal wire frame or some other carrier could be also be used. Secondary optics or reflectors may be provided over and around the LEDs to shape the total light output of the linear LED array. Multiple LED arrays, or strips of LEDs can be combined in one lamp. For example, if LEDs with nontransparent substrates are used, multiple arrays with the substrates facing inward and the light emitting layers of the chips facing outward in different directions can be used to achieve the omnidirectional pattern. An array of LED devices can be twisted into a pattern, such as a helix, or two arrays or strips can be arranged as a double helix, the arrays form intersecting helical coils. Many other arrangements are possible.
It should also be recognized that the term “omnidirectional” and the phrase “substantially omnidirectional” are interchangeable for purposes of this disclosure, and neither term is intended to invoke complete or near complete uniformity of a light pattern. Rather, any pattern that avoids a completely dark area that might otherwise be present due to a mechanical mounting structure or a heat sink could be said to be omnidirectional or substantially omnidirectional within the meaning of the terms as used herein. In embodiments of the invention, some variation of light output around a lamp tube as described might be expected due to reduced transmission through a substrate, placement of multiple arrays of LED devices, and the like.
FIG. 2 illustrates another example of a lamp according to example embodiments of the present invention. Lamp 200 of FIG. 2 again includes a tubular enclosure 202 . As before, the tubular enclosure can be made of glass, plastic, or any other suitable material. Within this lamp again is a linear array of LED devices 206 , which are energized through electrical connections. As before, the linear array of LED devices can be a plurality of individual LED chips simply connected together by conductive glue, solder or welds. Different color LEDs can be mixed together to create white light. Tubular enclosure 202 of lamp 200 is filled with an optically transmissive fluid medium 208 , such as a liquid or a gel, that has good thermal transfer properties and can provide cooling to the LED devices in the linear array.
Still referring to FIG. 2 , lamp 200 in this case includes an end cap power supply or power supplies 220 coupled to the linear array of LEDs through an electrical connection. Additional connection(s) 240 provide power to the power supplies, which are designed to convert the voltage provided by a light fixture to the voltage needed to supply the linear array of LEDs. In some embodiments, only one of the end caps of the lamp includes an active power supply, which powers to entire string of LEDs, while the other end cap simply allows the external pins to serve as mechanical support. In other embodiments, a power supply is contained in each of the end caps. Each supply in such a case can power a different linear array or different linear arrays of LEDs. For example, each can power an array of approximately half the length of the envelope's length installed end-to-end. Alternatively, if different arrays of the full length of the tube are installed, each power supply could be connected to a different array or arrays of LEDs.
It should be noted that lamp 200 of FIG. 2 could be of various lengths, and that only ends are shown for the sake of clarity and convenience of illustration. Such a lamp can be used as a replacement for a standard fluorescent tube that is commonly found in ceiling fixtures, desk lamps or task lights. In such a case, power supplies 220 would be designed to accommodate the voltage output during startup and operation by such a fixture as originally intended for a fluorescent bulb. Such an embodiment would be directed at retrofitting fixtures that use lamp types T8 or T12, such as those manufactured by G.E., Westinghouse or Sylvania. For example, some such common office ceiling fixtures use four T-12 lamps. The diameter of tubular enclosure 202 and end cap power supplies 220 would also vary according to the bulb to be replaced. As a note, a T12 fluorescent lamp has a 12/8-inch diameter tube, and a T8 fluorescent lamp has an 8/8-inch diameter tube.
In order to more fully explain the various embodiments of the present invention, further details of various possible embodiments will now be discussed. With respect to the fluid medium used, as an example, a liquid, gel, or other material that is either moderate to highly thermally conductive, moderate to highly convective, or both, can be used. As used herein, a “gel” includes a medium having a solid structure and a liquid permeating the solid structure. A gel can include a liquid, which is a fluid. The term “fluid medium” is used herein to refer to gels, liquids, and any other non-gaseous, formable material. The fluid medium surrounds the LED devices in the tubular enclosure. In example embodiments, the fluid medium is nonconductive enough so that no packaging or insulation is needed for the LED devices, although packaging may be included. In example embodiments, the fluid medium has low to moderate thermal expansion, or a thermal expansion that substantially matches that of one or more of the other components of the lamp. The fluid medium in at least some embodiments is also inert and does not readily decompose.
As examples, a fluid medium used in some embodiments may be a perfluorinated polyether (PFPE) liquid, or other fluorinated or halogenated liquid, or gel. An appropriate propylene carbonate liquid or gel having at least some of the above-discussed properties might also be used. Suitable PFPE-based liquids are commercially available, for example, from Solvay Solexis S.p.A of Italy.
As previously discussed, since LEDs typically emit light of a single color or wavelength, it is often desirable to mix multiple LED chips, each emitting a different color of light within a device or within a lamp such as the linear LED lamp of embodiments of the invention. As an example, devices emitting red, green and blue (RGB) light can be used to form substantially white light. As another example, red and blue-shifted yellow (R+BSY) devices might be used together to create substantially white light. If two types of LEDs are used to generate white light, an array of each type of LED can be arranged in the lamp so that the two arrays form the double helix previously discussed.
Since the different color-emitting LED chips in such examples must necessarily be separated in space, even if by very tiny amounts, it may be desirable to add color mixing treatment to the linear lamp in some embodiments to eliminate any color tint that may otherwise appear in parts of the light pattern from the lamp. Color mixing treatment can consist of or include frosting or texturing of the tubular enclosure of the lamp. As additional examples, FIGS. 3 and 4 show embodiments of the lamp in which a color mixing treatment is disposed inside the tubular enclosure of the lamp.
FIG. 3 illustrates a lamp 300 using strips of open cell foam as a color mixing treatment. Lamp 300 of FIG. 3 includes tubular enclosure 302 with electrical connections 304 . Within the lamp is a linear array of LED devices 306 , which are energized through electrical connections 304 . Tubular enclosure 302 is filled with an optically transmissive fluid medium 308 , such as a liquid or a gel, that has good thermal transfer properties and can provide cooling to the LED devices in the linear array, as previously discussed. Lamp 300 also includes strips of open cell foam, 312 . The open cell foam acts as a light diffuser and therefore serves as a color mixing treatment. The fluid medium fills the foam and maintains the thermal properties necessary to cool the LED devices in the linear array. For clarity, only two strips of open cell foam are shown, however, multiple strips may be placed around the LED array, or a continuous tube of open cell foam may be used in the lamp.
FIG. 4 illustrates a lamp 400 using nanowires as a color mixing treatment. Nanowires are very thin wires, which can be hollow. Nanowires as thin as one nanometer have been produced, but nanowires used in typical commercial applications as of this writing are between 30 and 60 nanometers wide. Lamp 400 of FIG. 4 includes tubular enclosure 402 with electrical connections 404 . Within the lamp is a linear array of LED devices that are energized through electrical connections 404 . Tubular enclosure 402 is filled with an optically transmissive, index matching fluid medium 408 , such as a liquid or a gel, that provides cooling to the LED devices in the linear array, as previously discussed. Lamp 400 also includes hollow nanowires 416 . The refractive index of the nanowire does not match the fluid medium and so the nanowires act as a light diffuser and therefore serve as a color mixing treatment. The fluid medium fills the nanowires and maintains the thermal properties necessary to cool the LED devices in the linear array. For clarity, nanowires are only shown on two sides of the linear array of LED devices in FIG. 4 , however, in a typical embodiment, nanowires would be distributed around the LED array.
It should be noted that as an alternative to producing white light by using LED chips that emit different colors and color mixing treatment, an LED linear lamp according to embodiments of the invention can be designed to use phosphor to emit light. With such a lamp, an array of single-color LED devices would be used, for example, blue, violet, or ultraviolet emitting LED chips. The tubular enclosure of the lamp in this case can be made of glass and the glass can be coated with phosphor that emits substantially white light when energized by the light from the LEDs. It should also be noted that elements of the various embodiments can be combined in ways other than those shown. For example, any or all of the color mixing treatments described above can be used with a lamp that includes power supplies like the lamp shown in FIG. 2 .
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof. Additionally, comparative, quantitative terms such as “less” and “greater”, are intended to encompass the concept of equality, thus, “less” can mean not only “less” in the strictest mathematical sense, but also, “less than or equal to.”
It should also be pointed out that references may be made throughout this disclosure to figures and descriptions using terms such as “up”, “inward”, “outward”, “down”, “side”, “top”, “in”, “within”, “on”, and other terms which imply a relative position of a structure, portion or view. These terms are used merely for convenience and refer only to the relative position of features as shown from the perspective of the reader. An element that is placed or disposed atop another element in the context of this disclosure can be functionally in the same place in an actual product but be beside or below the other element relative to an observer due to the orientation of a device or equipment. Any discussions which use these terms are meant to encompass various possibilities for orientation and placement.
Although specific embodiments have been illustrated and described herein, those of ordinary skill in the art appreciate that any arrangement which is calculated to achieve the same purpose may be substituted for the specific embodiments shown and that the invention has other applications in other environments. This application is intended to cover any adaptations or variations of the present invention. The following claims are in no way intended to limit the scope of the invention to the specific embodiments described herein.
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A linear LED lamp is disclosed. Embodiments of the invention can provide an LED-based replacement lamp for a linear or “tube-type” bulb or a bulb with a linear filament or element. By filling the void within the lamp with an optically transmissive fluid to cool the LEDs without the use of a traditional heat sink, the light blocking effects of such a heat sink can be avoided. Thus, the LED replacement lamp can emit light in a substantially omnidirectional pattern. In some embodiments, the optically transmissive fluid medium is a liquid. In some embodiments, the optically transmissive fluid medium is a gel. An index matching medium can be used as the optically transmissive fluid medium. A color mixing treatment can optionally be included to eliminate color tints in cases where multiple LEDs of different colors are used to produce white light.
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FIELD OF THE INVENTION
This invention relates to a panel testing apparatus and method for non-destructive testing of structural panels for stiffness and strength which finds particular application in testing of composite wood panels or boards.
BACKGROUND OF THE INVENTION
In the production of composite wood panels or boards such as waferboard, plywood, oriented strand board (OSB), particleboard, medium density fibreboard (MDF) and the like, it is desirable to monitor the stiffness and strength of the end product which are typically flat sheets. The stiffness (EI) or the modulus of elasticity (MOE), which can be derived from stiffness, provide an indication of the ultimate strength or modulus of rupture (MOR) of the panel. Since composite wood panels and boards are generally formed on an assembly line, it is also desirable to have testing done at the output end of the assembly line in a testing unit designed for high speed operation.
It is possible to take individual selected panels off the assembly line and subject them to appropriate testing, however, this testing scheme tends to introduce a delay between production and testing and does not lend itself to efficient feedback control for the manufacturing process.
Prior art equipment exists for automatically testing panels or lumber as they exit the production line. This existing equipment generally performs testing by bending of the material. Bending can be done by introducing the panel or lumber into an "S" shaped path. The material is forced to deflect a given amount in its elastic range in two opposite directions and the resultant forces are measured using load cells to determine panel stiffness. The "S" shaped testing method produces an average panel stiffness of both sides of the test panel and assumes a linear stiffness response of the test panel. Examples of prior art testing apparatus and methods that rely on the deflection of the panel or lumber into an "S" shape are U.S. Pat. No. 3,196,672 to Keller and U.S. Pat. No. 4,708,020 to Lau et al.
An alternative to "S" shaped bending of the panel is to subject the panel to bending by applying forces to distort the panel sequentially to two given deflections on the same side of the panel while simply supporting the ends of the panel. This technique can be referred to as "W" shaped bending as the two sequential bending tests, when imagined side by side, distort the panel into a shallow "W" shape. The load to produce each of the given deflections is monitored and the panel stiffness and modulus of elasticity can be determined by the slope of the load-deflection curve. Examples of prior art testing equipment that relies on "W" shaped bending of the panel are U.S. Pat. No. 4,722,223 and U.S. Pat. No. 5,804,738 both to Bach et al. To avoid non-linear regions of the load-deflection curve, two points along the linear region are used to determine the slope rather than relying on one data point and the origin. Preferably, the two data points are determined by applying a first small pre-load of approximately 10% of the ultimate load for the panel, and then applying a final load of approximately 30% of the ultimate load.
Unlike "S" shape bending which measures stiffness based on both sides of the panel, "W" shape bending measures the panel stiffness from one side of the panel corresponding to the intended load bearing side of the panel. Test results indicate that there can be a difference in panel stiffness of up to 6% between opposite sides. Therefore, the "W" shaped bending test is the preferred method for determining the stiffness of load bearing panels.
SUMMARY OF THE INVENTION
Applicant has developed a compact panel stiffness testing apparatus and method that relies on the above described "W" shape bending test. However, to perform the "W" shaped bending test at high speed in order to keep up with production of panels on existing assembly lines, applicant has developed an apparatus and method that directs the panels undergoing testing along an essentially "C" shaped path while conducting the load and deflection measurements of the "W" shaped bending test. The apparatus of the present invention machine can be placed in panel production line so that testing can be done frequently or continuously as the panels are produced with little or no disruption of the assembly line.
Accordingly, in a first aspect the present invention provides apparatus for non-destructively testing the stiffness of panels having opposed panel surfaces and ends comprising:
a support framework;
infeed, centre and outfeed support assemblies mounted to the framework in spaced, successive positions, each support assembly being adapted to contact the opposed panel surfaces of each panel to define a travel path along which the panel is advanced through the assembly;
a first deflection member intermediate the infeed and centre support assemblies movable to contact one of the panel surfaces as each panel extends between the infeed and the centre support assemblies with one end of the panel being supported by the infeed support assembly and the opposite end being supported by the centre support assembly, the first deflection member acting to bend the panel to a first pre-determined curvature;
a second deflection member intermediate the centre and outfeed support assemblies movable to contact the same one of the panel surfaces as each panel extends between the centre and the outfeed support assemblies with one end of the panel being supported by the centre support assembly and the opposite end being supported by the outfeed support assembly, the second deflection member acting to bend the panel to a second pre-determined curvature;
load cells associated with the first and second deflection members to measure the force require to bend the panels to the pre-determined curvatures for calculation of the stiffness of the panels;
whereby the infeed, centre and outfeed support assemblies are movable relative to each other to position the support assemblies such that the travel paths through the support assemblies define a generally "C" shaped path through the apparatus that accommodates the curvatures that each panel adopts in travelling through the apparatus.
In a further aspect, the present invention provides a method for non-destructively testing the stiffness of a panel having first and second panel surfaces comprising:
feeding the panel through first, second and third spaced support assemblies positioned with respect to each other to define a generally "C" shaped path of travel for the panel that accommodates the curvatures that the panel will adopt;
deflecting the panel by a first pre-determined amount by applying a deflecting force to a surface of the panel as the panel passes between the first and second support assemblies with the ends of the panel being supported by the first and second support assemblies;
deflecting the panel by a second pre-determined amount by applying a deflecting force to the same surface of the panel as the panel passes between the second and third support assemblies with the ends of the panel being supported by the second and third support assemblies;
measuring the force required to deflect the panel by the pre-determined amounts; and
calculating the stiffness of the panel using the force and deflection data.
The apparatus and method of the present invention permit high speed testing of panels at speeds of up to 600 feet per minute for 5/16 inch thickness panels to match the production speed of state-of-the-art plants.
The panel testing apparatus can accommodate up to ±1/16 inch thickness variation in a panel.
The apparatus tests the panels using the mid-span loading and simply-supported end conditions of the preferred "W" shaped bending test while moving the panels along an essentially "C" shaped path.
BRIEF DESCRIPTION OF THE DRAWINGS
Aspects of the present invention are illustrated, merely by way of example, in the accompanying drawings in which:
FIG. 1 is a side elevation view of a preferred embodiment of the panel stiffness testing apparatus of the present invention;
FIG. 2 is a top plan view of the apparatus of FIG. 1;
FIG. 3 is an end view of the apparatus of FIG. 1;
FIG. 4 is a detail plan view of a typical support assembly according to the present invention;
FIG. 5 is a detail elevation view of the support assembly of FIG. 4;
FIG. 6 is a detail view of the screw jack system for adjusting the separation of the upper and lower rolls of the support assembly taken along line 6--6 of FIG. 4;
FIG. 7 is detailed end view showing the manner in which the position of the support assemblies is adjusted;
FIG. 8 is a detail elevation view showing the screw jacks used to adjust the position of the support assemblies;
FIG. 9 is a detail elevation view of showing the deflection members of the present invention;
FIG. 10 is a detail elevation view of the link structure associated with the deflection members;
FIG. 10a is a detail end view of a deflection member;
FIG. 11 is a schematic view showing the bending tests conducted by the method and apparatus of the present invention; and
FIG. 12 is a schematic view showing the deflection of a panel in the apparatus of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1, 2 and 3, there are shown elevation, plan and end views, respectively, of a preferred embodiment of a non-destructive panel stiffness tester 2 according to the present invention. Tester 2 comprises includes a rigid external support framework 4 which encloses the working components of the apparatus. Support framework 4 is comprised of a series of structural beams selected for their stiffness that are welded together to create a rigid platform. As best shown in FIG. 3, the top half of frame 4 is preferably covered by hinged doors 6 to allow access to the major internal components of the tester for removal, replacement or maintenance.
Referring to FIGS. 1 and 2, panels to be tested are introduced at input end 8 of apparatus 2 to be handled by infeed, centre and outfeed support assemblies 10, 12 and 14, respectively, and discharged from output end 16. The direction of panel flow through the apparatus is indicated by arrow 9 in FIGS. 1 and 2. Panel support assemblies 10, 12, and 14 are mounted to rigid framework 4 in spaced, successive positions. Each support assembly is adapted to contact the opposed surfaces of each panel being tested to define a travel path along which a panel is advanced through the apparatus. Also mounted within framework 4 are deflection members 17 and 18 positioned to apply a deflecting force to a panel as it passes between adjacent panel support assemblies.
The panel support assemblies 10, 12 and 14 share a common construction best shown in detail in FIGS. 4, 5 and 6. Each support assembly includes an upper group 20 of four rolls 24 and a lower group 22 of four rolls 24. As shown in FIG. 4, the ends of each roll 24 are rotatably supported by bearing blocks 25. The first and last rolls, or outer rolls, of upper roll group 20 are supported by separate bearing blocks while the two inner rolls are supported by a combined bearing block. Upper beams 30 extend adjacent the upper group 20 of rolls. The ends of each of the upper group 20 of rolls 24 are mounted by bearing blocks 25 to the underside of beam 30 by biasing means in the form of air bags 32. Individual airbags support the ends of each of the outer rolls while the ends of the two inner rolls are each supported by a single airbag. Upper beams 30 are joined by upper cross members 29 to create a generally rectangular upper frame 20a supporting the upper group 20 of rolls. In a similar manner, lower side plates 28 support the bearing blocks 25 that retain the lower group 22 of rolls, and lower cross members 32 join the lower side plates 28 to create a lower frame 22a supporting the lower group 22 of rolls.
The upper and lower groups 20, 22 of rolls are spaced apart to create a gap or nip therebetween that defines the travel path 35 of the panels through each panel support assembly. The lower group of rolls are all driven as are the outer rolls of the upper group, hence the individual bearing blocks and airbags for the upper outer rolls. The driven rolls are powered by a conventional multiple toothed belt drive from an AC synchronous motor through a servo drive (not shown).
The upper and lower groups of rolls act to clamp the panels undergoing testing between the rolls and advance the panel through the assembly. Airbags 32 that support the rolls of upper roll group 20 exert the required clamping force on the panels against the lower group 22 of rolls. Airbags 32 also allow the rolls of upper group 20 to accommodate any local variations in panel thickness. As mentioned previously, the outer rolls of upper group 20 are attached to an individual pair of airbags whereas the inner pair of upper rolls share a pair of airbags. Preferably, the inner pair of upper rolls are loaded to a maximum of 500 pounds nip force to provide the necessary traction on the panel. The outer top rolls, however, will experience the nip forces and the reaction forces from the panel bending between adjacent support assemblies. For example, in the case of the outer top rolls in the centre and outfeed support assemblies, the airbags must be able to withstand a total maximum force of approximately 2000 pounds. The air pressure to the airbags are therefore set at different levels according to the position of the rolls. In addition, airbag pressure is also adjustable to suit different panel thickness settings. Thicker panels develop greater reaction forces as they are deformed and also require higher nip forces. The various air bag pressure settings can be preprogrammed and automatically set when a given panel thickness setting is input.
The roll groups of the infeed and centre support assemblies are equipped with over-running clutches. The drive speeds of the roll groups of all the panel support assemblies are also selected so that each successive group of rolls runs slightly faster (approximately 0.5%) than the preceding group. When a panel passes out of the roll groups in the infeed support assembly and between the roll groups of the centre support assembly, the panel will speed up slightly once it is fully gripped between the rolls of the centre support assembly. The panel is thus caused to move through the infeed support assembly at a higher speed than the driven speed of the infeed groups of rolls. Therefore, the over-running clutch for the infeed support assembly will be over-run so that, in effect, the drive for the infeed groups of rolls are disengaged and the panel is driven solely by the rolls of the centre support assembly. The drag on the panel created by the infeed rolls rotating over the panel surface has been determined to be sufficiently low that only very low tension force are generated in the panel. If necessary, since the drag on the panel should be at a constant, predictable level then compensation can be provided in the calculations of the panel stiffness using data conditioning algorithms.
The process outlined above will be repeated when the panel passes from the centre support assembly to the outfeed support assembly. In this case, the panel will begin to move at the faster speed of the outfeed support assembly and the over-running clutch of the centre support assembly will disengage the drive for the groups of rolls in the centre support assembly.
Prototype testing has shown that slight differences in drive speeds between the roll groups of adjacent support assemblies can have an adverse impact on the load readings for a panel, particularly for thin panels (the thinnest panel being 5/16 inch thick). A difference in drive speeds can put a panel in tension or compression and this creates an error in the load reading. The foregoing over-running clutch system, which effectively disengages the drive of a preceding roll group when driving of the panel is taken up by the subsequent roll group, assures that undesirable compressive and tensile stresses will not be developed.
To accommodate panels of different thicknesses, the spacing of the upper and lower roll groups is adjustable. This is accomplished by virtue of extendable connections in the form of machine screw jacks 40 that reach between the upper and lower frames supporting upper and lower roll groups 20 and 22, respectively. Referring to FIGS. 4 and 6, screw jacks 40 are positioned at the four corners of the upper frame 20a. Screw shafts 42 extend downwardly from each jack body to connect the upper frame 20a to lower frame 22a. The screw jacks 40 are driven together as a group via drive system 44 to set the desired gap between the upper and lower groups of rolls.
The infeed, centre and outfeed support assemblies 10, 12 and 14, respectively, of the apparatus of the present invention are movable with respect to each other to position and align the travel paths 35 of each support assembly to define a generally "C" shaped path that extends through the entire apparatus. Such a path allows the panels being tested to be fed quickly and efficiently through the apparatus. The support assemblies are positioned with respect to each other such that a panel leaving one support assembly is automatically aligned with the subsequent support assembly. FIG. 11 schematically shows the travel path of panels 50 through the roll groups of each support assembly 10, 12 and 14 and past the deflection members 17 and 18 of the panel tester of the present invention.
Referring to FIG. 1, in the illustrated preferred embodiment, relative movement of the various support assemblies is achieved by mounting centre support assembly 12 rigidly to support framework 4 and mounting infeed support assembly 10 and outfeed support assembly 14 to framework 4 for movement. The infeed and outfeed support assemblies are mounted to framework 4 by adjustable mounts to permit variation in the positions of the assemblies to maintain the generally "C" shaped travel path through the apparatus for different thicknesses of panel.
As best shown in FIGS. 7 and 8, the adjustable mounts preferably comprise screw jacks 60 that extend from adjacent the four corners of lower frame 22a of each support assembly to main framework 4. Each screw jack 60 is pivotally mounted at its connection to the lower frame 22a and to framework 4. Screw jacks 60 are coupled together into pairs via drive shafts 62 at the ends of each support assembly 10 and 14 to permit control of the ends of each support assembly. Preferably, jacks 60 are driven by means of computer controlled servo drives to position the infeed and outfeed support assemblies to the correct settings for a particular thickness of panel to ensure a smooth "C" shaped path through the entire apparatus.
As best shown in FIGS. 9, 10, and 10a, deflection members 17 and 18 are mounted between infeed support assembly 10 and centre support assembly 12, and between centre support assembly 12 and outfeed support assembly 14, respectively. Each deflection member is preferably a roll 65 supported at each end by a bearing block 67 that is in turn mounted atop a load cell 68. Each load cell 68 is mounted to a ball screw jack 70 that is pivotally mounted to support framework 4. As best shown in FIG. 10a, the pair of screw jacks 70 that support the ends of each roll 65 are joined by a drive shaft 72 that is powered by servo motor 73. Motor 73 operates to position deflection roll 65 to contact the lower surface of a panel as the panel travels between the infeed and centre support assemblies (stage 1) or between the centre and outfeed support assemblies (stage 2). The function of deflection rolls 65 is to bend the panel to a pre-determined curvature at each stage and provide a loading point at approximately the centre of each stage with the opposite ends of the panel being supported by the support assemblies between which the panel extends. At the same time, the infeed support assembly and the outfeed support assembly are positioned relative to the centre support assembly such that the travel paths 35 through all the assemblies generally coincide with the generally curved natural path of travel described by a panel of a particular thickness.
The actual load developed at the panel as a result of its bending (up to a maximum of approximately 3000 pounds at stage 2) is measured by load cells 68. Deflection member 18 at stage 2 is preferably positioned to develop a panel curvature that is in the order of three times greater than that at stage 1.
Referring to FIG. 10, each deflection member 17, 18 includes a link structure 80 comprising a pair of arms 82 extending in opposite directions. Arms 82 are mounted to the top of screw jack 70 to move with the jack. Arms 82 of link structure 80 span the distance between the adjacent support assemblies. The ends of arms 82 are formed with apertures 83 that engage about the bearing journals supporting the ends of each of the outer rolls 86 of the lower roll group 22 in each panel support assembly 10, 12 or 14 (FIG. 9). In this manner, link structure 80 serves to connect the support assemblies together so that drive centre distances for the belt driven rolls remain fixed when an adjustment of the position of the infeed or outfeed panel support assemblies is made.
Referring to FIGS. 1 and 3, there is preferably a by-pass conveyor 90 that runs along the entire length of main framework 4 below the panel support assemblies. This conveyor provides an alternative path for the panels 50 through the apparatus while a jam is being cleared from the main travel path through the panel support assemblies or while the apparatus is otherwise not in operation.
The operation of the panel tester of the present invention is maintained and controlled by a computer system that also stores and outputs required panel stiffness data. The operator is required to input the desired panel thickness into the computer to set the apparatus for the correct panel thickness. The computer then sends appropriate positioning commands to the various jacks to set up the machine. Output data from load cells 68 are processed using a series of specially developed algorithms to determine panel stiffness and the panel stiffness data is displayed and/or stored for trending analysis.
In operation, panels to be tested 50 are fed by a conveyor system (not shown) to input end 8 of the apparatus (see FIG. 1). The upper and lower roll groups 20 and 22, respectively, of infeed support assembly 10 clamp and advance the panel along travel path 35 between the roll groups to the centre panel support assembly 12. As the leading edge of the panel 50 emerges from infeed support assembly 10 and is advanced to centre support assembly 12, deflection roll 65 of first deflection member 17 engages the lower surface of the panel. As previously explained, based on the thickness of the panel being tested, the elevation and angle of infeed support assembly 10 are adjusted relative to the centre support assembly 12 to feed panel 50 along a path that substantially coincides with the natural panel curvature between the assemblies and the leading edge of the panel is advanced smoothly and guided to be received between the upper and lower roll groups of centre support assembly 12. To facilitate the efficient movement of the panels between adjacent support assemblies, guide arms 92 extend forwardly from each support assembly (FIG. 1 and 2) to assist in guiding the leading edge of each panel.
The purpose of the panel testing apparatus of the present invention is to replicate the simply supported panel deflection test conditions of the previously discussed "W" shaped bending test at high speed and in a compact space. As illustrated schematically in FIG. 11, this is achieved in the following manner: once panel 50 extends between infeed support assembly 10 and centre support assembly 12, the panel is effectively simply supported at both ends by rolls 100 and 101 with the remaining rolls of the support assemblies supporting and isolating the panel weight and any vibration. The roll of deflection member 17 acts to deform panel 50 to a pre-determined induced curvature and load cells associated with the deflection member record the load experienced by the panel. In a similar manner, panel 50 is then advanced from centre support assembly 12 to outfeed support assembly 14. Deflection member 18 is positioned to exert a greater pre-determined curvature to panel 50 than in stage 1 and outfeed support assembly 14 is positioned in the path of the leading edge of the panel. Rolls 104 and 105 effectively simply support the ends of the panel and the load cells associated with deflection member 18 record the load that the panel is subject to.
The panel testing apparatus of the present invention is designed to test panel thicknesses in the range between 5/16 inch to 11/4 inches. Ideally, the position of the infeed and outfeed support assemblies would be set according to the actual panel thickness. For practical reasons, this is not possible and the panel thicknesses are therefore preferably grouped into eight thickness groups of 1/8 inch increments. The apparatus tests all panel thicknesses within a given thickness group using the same apparatus settings relating to the gap between roll groups and the elevation and angle of the infeed and outfeed support assemblies. For a given thickness group, the apparatus is set to accommodate the simply supported conditions of the mean thickness panel for the group. As a result, an error exists for all other thicknesses within the group. The thickness group for 5/16 inch to 7/16 inch thick panels are most sensitive to this error because of the relatively low deflection force readings for these thinner panels. Finite Element Analysis (FEA) has been performed to assess the magnitude of the error for the worst case of a 5/16 inch thick panel. The results of the analysis indicate that by using the theoretical span and deflection for a given thickness in each thickness group to calculate panel stiffness, the error due to imperfect set up conditions of the apparatus is insignificant, that is, a maximum error of about 0.01% in load readings. Therefore, the positioning of the infeed and outfeed support assemblies for groups of panel thicknesses at increments of 1/8 inch between groups does not adversely affect the stiffness measurements generated by the apparatus of the present invention.
Based on prototype testing, applicant has developed a general formula to calculate stiffness based on the measurements acquired by the apparatus of the present invention according to equation 1 as follows:
Stiffness=EI=(Load*Span.sup.3)/(48*Deflection) (1)
where
Load=the measured deflection force
Span=L=the distance between the supported ends of the panel
Deflection=D=the distance the deflection roll is moved to establish the pre-determined curvature of the panel
The above parameters are shown in FIG. 12 which is a schematic view showing the deflection of a panel between adjacent stages of the apparatus of the present invention. It will be noted that the machine span L and machine deflection D are not the same as the true span L T and the true deflection D T . It is desirable to use the true span and deflection to obtain the most accurate stiffness readings.
Examples of machine settings for stages 1 and 2 of the apparatus of the present invention are as follows:
______________________________________ Stage 1 Stage 2 Stage 1 Stage 2Thickness Mean Panel Deflection Deflection Theta ThetaGroup Thickness (inch) (inch) degrees degrees______________________________________1 3/8" 0.35 1.00 1.6685 4.74702 1/2" 0.25 0.75 1.1925 3.56703 5/8" 0.20 0.60 0.9540 2.85604 3/4" 0.16 0.50 0.7635 2.38155 7/8" 0.14 0.42 0.6680 2.00156 1" 0.12 0.37 0.5725 1.76357 11/8" 0.11 0.33 0.5250 1.57308 17/32" 0.10 0.30 0.4775 1.4305______________________________________
For a given panel thickness, the true deflection and span can be computed using equations 2 and 3 as follows:
True Deflection=D.sub.T =D+[R+T/2) -(R+T/2)cosine(Theta)] (2)
True Span=L.sub.T =L+(2R+T)sine(Theta) (3)
where D is the machine deflection in inches
L is the machine span in inches=36"
R is the roll radius in inches=2.865"
T is the nominal panel thickness in inches
Theta is the angle indicated in FIG. 12
Equation 4 below can be used for computing the panel stiffness of a specific panel location. Equation 5 can be used for computing the average stiffness of a panel.
Panel Stiffness=EI=[(P.sub.2 *L.sub.T2.sup.3) -(P.sub.1 *L.sub.T1.sup.3)]/[48*(D.sub.T2 -D.sub.T1)] (4)
where
P 1 is the measured force at stage 1 for a specific panel location
P 2 is the measured force at stage 2 for the same location as P 1
L T1 is the true span of stage 1
L T2 is the true span of stage 1
D T1 is the true deflection of stage 1
D T2 is the true deflection of stage 1
Average Panel Stiffness=[SUM(EI.sub.i).sub.(i= 1 to n)]/n (5)
where
EI i is the panel stiffness for location i as per equation (4)
n is the number of panel locations
As indicated above in formula (4), the panel stiffness is determined based on the difference of the load readings between stages 2 and 1 for the same panel location. Preferably, the computer control system is set to sample load data at both stage 1 and stage 2 at 25 points along the center five feet length of an eight foot panel.
The various panel support assemblies of the present invention have been designed to provide decoupling between the stage 1 and stage 2 deformation testing of the apparatus of the present invention. The panel support assemblies also provide decoupling between the testing stages and the outside world. This ensures that there is no interaction between the operation of one testing stage with another. This also ensures that anything happening to the panels as they enter or leave the panel tester will not effect the stiffness measurements. It has been determined by using Finite Element Analysis (FEA) that four pairs of rolls are preferably employed in each roll group of the support assemblies to provide the decoupling described above. A further benefit of the support assembly design of the present invention is vibration isolation between each support assembly so that impulses resulting from a panel edge entering the first pair of rolls in a support assembly are not detected by the load cells in the next stage. It has been determined that use of a low pass filter to cut out noise above 5 hertz will provide better and more accurate load measurements. This is based on prototype test results indicating that the frequency of panel stiffness variability does not exceed 5 hertz within a panel along its length. The natural frequencies of OSB panels were measured and determined to be in the range of 7.65 hertz to 14.75 hertz for 3/8 inch to 11/8 inch thick panels, respectively, under mid-point loading of a simply supported span of 44 inches. The natural frequencies of OSB panels for a span of 36 inches, as is the case with the panel testing apparatus of the present invention, and constrained under the boundary conditions of the apparatus can be expected to be higher and are estimated to be in the range of 10 to 20 hertz. The natural frequency of the apparatus was designed to be relatively high (35 hertz and above) so that use of a low pass filter is able to isolate the measurement frequency domain from any panel or machine natural vibration frequencies.
The computer control system of the apparatus of the present invention has also been designed to recover gracefully from a panel jam within the panel support assemblies. In the event of a jam, the computer activates jacks 60 supporting the infeed 10 and outfeed 14 panel support assemblies to fully extend the jacks so that these support assemblies are positioned horizontally and in-line with fixed centre support assembly 12. Jacks 70 associated with deflection members 17 and 18 are retracted to drop rolls 65 to their lowest position so that the rolls are in the same plane or lower than the lower roll groups 22 in the support assemblies. Jacks 40 positioned between the upper 20 and lower 22 roll groups are then fully extended so that the space between the roll groups is maximized. Any panel jammed in the apparatus will then be completely free of any constraints and can be withdrawn by hand.
Although the present invention has been described in some detail by way of example for purposes of clarity and understanding, it will be apparent that certain changes and modifications may be practised within the scope of the appended claims.
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Apparatus and method for non-destructively testing the stiffness of wood panels. The apparatus comprises a support framework having infeed, center and outfeed support assemblies mounted to the framework in spaced, successive positions. Each support assembly is adapted to contact the opposed panel surfaces of each panel to define a travel path along which the panel is advanced through the assembly. A first deflection member is provided intermediate the infeed and center support assemblies and is movable to contact one of the panel surfaces as each panel extends between the infeed and the center support assemblies. The first deflection member acts to bend the panel to a first pre-determined curvature. In a similar manner, there is a second deflection member intermediate the center and outfeed support assemblies movable to bend the panel to a second pre-determined curvature. Load cells associated with the first and second deflection members measure the force require to bend the panels to the pre-determined curvatures for calculation of the stiffness of the panels. The infeed, center and outfeed support assemblies are movable relative to each other to position the support assemblies such that the travel paths through the support assemblies define a generally "C" shaped path through the apparatus that accommodates the curvatures that each panel adopts in travelling through the apparatus. The apparatus provides a compact panel testing unit by virtue of the "C" shaped travel path though the apparatus that is able to operate at the high speeds of a production line.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an LED (Light-Emitting Diode) driver, and more specifically to a programmable LED driver with an embedded non-volatile memory storing control data for custom programming of a variety of features of the LED driver.
[0003] 2. Description of the Related Arts
[0004] White LEDs are being used increasingly in display devices. For example, some modern liquid crystal display (LCD) devices use white LEDs as the backlight for the LCD display. These LEDs are typically driven by an LED driver. White LED drivers are typically constant current devices where a constant sink current is fed through the white LEDs to provide a constant luminescence. The anode of the white LEDs is driven by a charge pump circuit.
[0005] FIG. 1 illustrates a conventional LED driver 100 driving LEDs 112 , 114 . For example, the LEDs 112 , 114 can be white LEDs. The LED driver 100 includes 2 main circuit blocks, a charge pump 102 and a current regulator 110 . The charge pump 102 typically converts a battery voltage (V IN ) into an output voltage (V OUT ) coupled to the anodes of the LEDs 112 , 114 . The output voltage (V OUT ) drives the LEDs 112 , 114 .
[0006] Current through the LEDs 112 , 114 sets their intensity and associated luminescence. Thus, in order to obtain accurate intensity, which is very important for displays, the current through the LEDs 112 , 114 must be set accurately. Typically, the current regulator 110 is responsible for driving the LEDs with constant current. The current regulator 110 includes, among other components, a bandgap voltage generator 104 , an error amplifier comprised of the amplifier 106 and the transistor 119 , a current mirror 108 comprised of transistors 116 , 118 , and LED drive transistors 122 , 124 , 126 .
[0007] The bandgap voltage generator 104 generates a bandgap voltage Vref, and the error amplifier ( 106 , 119 ) ensures that the voltage at node 121 across the resistor R EXT 120 is set at Vref. Typically, the resistor R EXT 120 is external to the LED driver circuit 100 . The reference current I REF through the external resistor R EXT 120 is set by the bandgap voltage Vref and the external resistor R EXT 120 . That is, the reference current I REF is set by Vref/R EXT . The reference current I REF is repeated through the transistor 122 by the current mirror 108 , and eventually drives the LEDs 112 , 114 by the transistors 122 , 124 and the transistors 122 , 126 , respectively. The size (W/L ratio, or width/length ratio) of the transistors 124 , 126 relative to the size of the transistor 122 determines how large the current I D1 , I D2 through the LEDs 112 , 114 is relative to the reference current I REF through the transistor 122 . Thus, the current I D1 , I D2 through the LEDs 112 , 114 is also determined by the bandgap voltage Vref and the external resistor R EXT 120 . The resistance R EXT of the external resistor 120 needs to be set accurately in order to control the luminescence of the LEDs 112 , 114 precisely. In conventional LED drivers 100 , there is no convenient way to change the current through the LEDs 112 , 114 without changing the resistance value of the resistor 120 .
[0008] Typical LED drivers 100 may use an external resistor 120 to set the current in the LEDs 112 , 114 . Such external resistor 120 adds a pin to the LED driver IC (integrated circuit), extra board space for the overall LED driver circuitry, and results in an increase in the Bill-of-Materials (BOM) cost for the overall LED driver circuitry. Note that different applications might require different maximum currents from the LED driver 100 . This is because different LEDs 112 , 114 from different manufacturers may give different intensity for different current values. With a conventional LED driver 100 , the only way to control the reference current I REF is to change the resistance value of the external resistor 120 so that the current through the LEDs 112 , 114 change accordingly. The resistor 120 is typically external to the LED driver 100 in order to have its resistance value changed, which results in waste of a pin, board space, and cost, as explained above.
[0009] The charge pump 102 typically operates in multiple operation modes. Initially at power up of the LED driver 100 , the input voltage V IN is attached to the output voltage V OUT via the charge pump 102 so that V IN equals V OUT . This mode is often called the 1× mode. The charge pump 102 typically changes operation modes as time goes by and the battery voltage V IN drops over time, because the LEDs 112 , 114 typically have a voltage drop. The typical voltage drop V LED in a white LED may be, for example, 3.4 V.
[0010] As the input voltage V IN decreases over the lifetime of the battery (not shown), the output voltage V OUT decreases in the same proportion since V IN equals V OUT when the charge pump is in 1× mode. Thus, the voltage at nodes 115 , 117 (the LED driver pins) is given by V OUT −V LED . When the voltage at nodes 115 , 117 becomes too low, typically 200 mV, the current regulator 110 goes out of saturation and can no longer provide an accurate current through the LEDs 112 , 114 . This causes the charge pump 102 to switch to a higher operation mode, typically a 1.5× mode that generates the output voltage V OUT to be 1.5×V IN . As a result, the LED driver pin voltage at nodes 115 , 117 rises high enough to push the current regulator 110 back into saturation. This process is repeated, and when the battery voltage V IN further decreases to cause the current regulator 110 to go out of saturation even under 1.5× mode, the charge pump switches to 2× mode that generates the output voltage V OUT to be 2×V IN .
[0011] Although the charge pump 102 may automatically switch to different operation modes as explained above, some LED applications may need to set the operation mode of the charge pump 102 to a single operation mode or have only selected ones of multiple operation modes, even when the charge pump 102 itself has circuitry to operate in multiple operation modes. In order to set the operation mode of the charge pump 102 in a conventional LED driver 100 , fixed circuitry has to be used in the charge pump 102 to permanently set the operation mode, which essentially requires manufacturing different LED driver integrated circuits using different metallization processes during the fabrication process of the LED driver IC.
[0012] Therefore, there is a need for a more convenient technique to change the maximum current through the LEDs. There is also a need for a technique to bring the resistor for generating the reference current internal to the LED driver and be able to trim the resistor. Finally, there is a need for a more convenient technique to set the operation mode of the charge pump of the LED driver.
SUMMARY OF THE INVENTION
[0013] Embodiments of the present invention include an LED driver with an embedded non-volatile memory (NVM) capable of being programmed and storing control data for setting a variety of features of the LED driver, such as but not limited to the maximum current for driving the LEDs, analog parameters such as the resistance of the internal resistor for setting the reference current for the LEDs, and operation modes of the charge pump of the LED driver. This enables the implementation of multiple LED driver product options without the need for different metallization steps during the fabrication process for the LED driver.
[0014] In one embodiment, a programmable LED driver for driving one or more LEDs comprises a charge pump configured to operate in one or more operation modes for receiving an input voltage and generating an output voltage to be applied to said one or more LEDs, a current regulator for generating a reference current, and a non-volatile memory module storing first control data, where current through the one or more LEDs is determined based on the reference current and the first control data.
[0015] In another embodiment, the current regulator includes a trimmable resistor internal to the programmable LED driver, and the reference current is generated based upon a reference voltage and the resistance of the trimmable resistor. The non-volatile memory further stores second control data, and the resistance of the trimmable resistor is adjusted based upon the second control data.
[0016] In still another embodiment, the charge pump is configured to operate in one or more of a plurality of operation modes, where each operation mode is configured to generate a different output voltage based on the input voltage. The non-volatile memory further stores third control data, and the one or more of the plurality of operation modes are activated or inactivated based upon the third control data.
[0017] The present invention has the advantage that a variety of features of the LED driver, such as the LED current, internal resistance for setting the reference current for the LEDs, and the operation modes of the charge pump, and potentially a variety of other analog parameters of the LED driver may be conveniently set simply by programming the LED driver with the appropriate control data value in the non-volatile memory. Thus, an LED driver with different functionalities and features can be implemented as a single IC from the same die in the semiconductor fabrication process without having to go through different metallization processes for the different functionalities during the fabrication of the IC for the LED driver.
[0018] The features and advantages described in the specification are not all inclusive and, in particular, many additional features and advantages will be apparent to one of ordinary skill in the art in view of the drawings, specification, and claims. Moreover, it should be noted that the language used in the specification has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The teachings of the embodiments of the present invention can be readily understood by considering the following detailed description in conjunction with the accompanying drawings.
[0020] FIG. 1 illustrates a conventional LED driver for driving LEDs.
[0021] FIG. 2 illustrates an LED driver for driving LEDs, according to one embodiment of the present invention.
[0022] FIG. 3 illustrates using the control data stored in the non-volatile memory (NVM) to trim the internal resistance of the LED driver, according to one embodiment of the present invention.
[0023] FIG. 4 illustrates the charge pump of FIG. 2 that is configurable using the control data stored in the NVM, according to one embodiment of the present invention.
DETAILED DESCRIPTION OF EMBODIMENTS
[0024] The Figures (FIG.) and the following description relate to preferred embodiments of the present invention by way of illustration only. It should be noted that from the following discussion, alternative embodiments of the structures and methods disclosed herein will be readily recognized as viable alternatives that may be employed without departing from the principles of the claimed invention.
[0025] Reference will now be made in detail to several embodiments of the present invention(s), examples of which are illustrated in the accompanying figures. It is noted that wherever practicable similar or like reference numbers may be used in the figures and may indicate similar or like functionality. The figures depict embodiments of the present invention for purposes of illustration only. One skilled in the art will readily recognize from the following description that alternative embodiments of the structures and methods illustrated herein may be employed without departing from the principles of the invention described herein.
[0026] FIG. 2 illustrates an LED driver 200 for driving LEDs 112 , 114 , according to one embodiment of the present invention. For example, the LEDs 112 , 114 can be white LEDs. The LED driver 200 includes 2 main circuit blocks, a configurable charge pump 201 and a current regulator 210 .
[0027] Current through the LEDs 112 , 114 sets their intensity and associated luminescence. The current regulator 210 is responsible for driving the LEDs 112 , 114 with constant current. The current regulator 210 includes, among other components, a bandgap voltage generator 104 , an error amplifier comprised of the amplifier 106 and the transistor 119 , a current mirror 108 comprised of transistors 116 , 118 , a non-volatile memory (NVM) 250 , and LED drive transistors 122 , 202 , 204 , 206 , 208 . Although the NVM 250 is shown in FIG. 2 as part of the current regulator 210 , the NVM 250 may be part of, or separate from, the current regulator 210 .
[0028] The NVM 250 stores control data for controlling the operation of various features of the LED driver 200 . For example, the NVM 250 stores control data A 1 , A 0 , B 1 , B 0 for controlling the current through the LEDs 112 , 114 , control data C 1 , C 0 for trimming the internal resistance R INT 220 , and control data D 2 , D 1 , D 0 for setting the operation mode of the charge pump 201 , as will be explained in more detail below. The control data A 1 , A 0 , B 1 , B 0 , C 1 , C 0 , D 2 , D 1 , D 0 stored in the NVM 250 may be 1-bit digital data, although they may be in other form of data. Such control data may be written into the NVM 250 via the write (WR) line 252 through, for example, an external computer (not shown). The data written into the NVM 250 are not deleted even when the NVM 250 is powered off. The NVM 250 can be a flash memory, an SRAM (Synchronous Random Access Memory), or any other type of non-volatile memory.
[0029] The bandgap voltage generator 104 generates a bandgap voltage Vref, and the error amplifier ( 106 , 119 ) ensures that the voltage at node 260 across the resistor R INT 220 is set at Vref. Note that the resistor 220 is internal to the LED driver 200 , contrary to the external resistor 120 for use with the conventional LED driver 100 of FIG. 1 . The reference current I REF through the internal resistor R INT 220 is set by the bandgap voltage Vref and the internal resistance R INT 220 . That is, the reference current I REF is set by Vref/R INT . The reference current I REF is repeated through the transistor 122 as current I REF ′ by the current mirror 108 , and eventually drives the LEDs 112 , 114 by the transistors 202 , 204 and transistors 206 , 208 , respectively.
[0030] The current I REF ′ through the transistor 116 may be identical to or different from the reference current I REF through the transistor 118 , depending upon the relative size or width/length (W/L) ratio of the transistor 116 compared to that of the transistor 118 . In addition, the current I REF ′ through the transistor 116 is repeated through the transistors 202 , 204 , 206 , 208 , according to their relative size or W/L ratio compared to that of the transistor 122 .
[0031] Note that the transistor 202 has a size or a width/length (W/L) ratio that is twice the W/L ratio of the transistor 204 , and the transistor 206 has a size or W/L ratio that is twice the W/L ratio of the transistor 208 . Thus, the transistor 202 draws twice as much the current drawn by the transistor 204 , both of which are added to drive the LED 112 . Likewise, the transistor 206 draws twice as much the current drawn by the transistor 208 , both of which are added to drive the LED 114 .
[0032] The control data A 1 , A 0 stored in the NVM 250 determine the maximum current through the LED 112 , and the control data B 1 , B 0 stored in the NVM 250 determine the maximum current through the LED 114 . Specifically, the control data A 1 , A 0 control the on/off state of the switches 210 , 212 , respectively. For example, the switches 210 , 212 may be on (closed) when the control data A 1 , A 0 are “1”, respectively, and off (open) when the control data A 1 , A 0 are “0”, respectively. The control data B 1 , B 0 control the on/off state of the switches 214 , 216 , respectively. For example, the switches 214 , 216 may be on (closed) when the control data B 1 , B 0 are “1”, respectively, and off (open) when the control data B 1 , B 0 are “0”, respectively.
[0033] For illustration, assume that the sizes or W/L ratios of all the transistors 118 , 116 , 122 , 204 , and 208 are identical, and the W/L ratio of the transistors 202 , 206 is twice the W/L ratio of the transistors 204 , 208 and that I REF is 1 mA. When A 1 , A 0 are “1” and “1” respectively, the maximum current through the LED 112 is 3 mA because both switches 210 , 212 are on. When A 1 , A 0 are “1” and “0” respectively, the maximum current through the LED 112 is 2 mA because the switch 210 is on and the switch 212 is off. When A 1 , A 0 are “0” and “1” respectively, the maximum current through the LED 112 is 1 mA because the switch 210 is off and the switch 212 is on. When A 1 , A 0 are “0” and “0” respectively, the maximum current through the LED 112 is 0 mA because both switches 210 , 212 are off. Similarly, when B 1 , B 0 are “1” and “1” respectively, the maximum current through the LED 114 is 3 mA because both switches 214 , 216 are on. When B 1 , B 0 are “1” and “0” respectively, the maximum current through the LED 114 is 2 mA because the switch 214 is on and the switch 216 is off. When B 1 , B 0 are “0” and “1” respectively, the maximum current through the LED 114 is 1 mA because the switch 214 is off and the switch 216 is on. When B 1 , B 0 are “0” and “0” respectively, the maximum current through the LED 114 is 0 mA because both switches 214 , 216 are off.
[0034] The resistance R INT of the internal resistance module 220 needs to be set accurately in order to control the reference current I REF and the luminescence of the LEDs 112 , 114 precisely. The use of an internal resistor 220 results in saving a pin of the LED driver IC and cost and board area associated with the additional pin. Since the resistor 220 is brought internal to the LED driver 200 according to the present invention, it should be capable of being trimmed internally and accurately as necessary. Although conventionally it was possible to use a polysilicon fuse to trim the internal resistor 220 , that has the disadvantage of increasing overall area and adding to manufacturing costs. Moreover, polysilicon or metal fuses have long term reliability problems due to fuse re-growth concerns.
[0035] FIG. 3 illustrates using the control data stored in the NVM 250 to trim the internal resistance module 220 , according to one embodiment of the present invention. Referring to both FIGS. 2 and 3 , the trimmable internal resistance module 220 of FIG. 2 includes a plurality of resistors connected in series with each other, in this example R 1 , R 2 , R 3 . The resistance module 220 also includes switches 302 , 304 that are connected in parallel to resistors R 2 , R 3 , respectively.
[0036] The switches 302 , 304 are turned on (closed) or off (open) in response to the control data C 0 , C 1 of the NVM 250 . For example, when the control data C 0 , C 1 are “1”, the switches 302 and 304 are turned on (closed), thereby shorting the connected resistors R 2 , R 3 , respectively. When the control data C 0 , C 1 are “0”, the switches 302 and 304 are turned off (open), and thus the resistors R 2 and R 3 become connected to R 1 in series. In other words, the switches 302 , 304 effectively remove or connect the corresponding resistors R 2 , R 3 , respectively to the resistor R 1 .
[0037] When C 0 is “1” and C 1 is “1”, the total resistance R INT =R 1 +R 2 +R 3 and I REF =Vref/(R 1 +R 2 +R 3 ). When C 0 is “1” and C 1 is “0”, the total resistance R INT =R 1 +R 2 and I REF =Vref/(R 1 +R 2 ). When C 0 is “0” and C 1 is “1”, the total resistance R INT =R 1 +R 3 and I REF =Vref/(R 1 +R 3 ). When C 0 is “0” and C 1 is “0”, the total resistance R INT =R 1 and I REF =Vref/R 1 . In this manner, the LED driver 120 of the present invention may trim the resistance R INT of the internal resistance module 220 and also set the reference current I REF through the internal resistor 220 and eventually the current through the LEDs 112 , 114 accurately without using fuses. The resistance R INT of the internal resistance module 220 and also set the reference current I REF through the internal resistor 220 are programmable simply by programming appropriate control data C 1 , C 2 of the NVM 250 that is internal to the LED driver 200 IC.
[0038] FIG. 4 illustrates the charge pump 201 of FIG. 2 that is configurable using the control data stored in the NVM 250 , according to one embodiment of the present invention. The configurable charge pump 201 converts a battery voltage (V IN ) into an output voltage (V OUT ) in one of the plurality of operation modes, a 1× mode, 1.5× mode, and 2× mode. The charge pump 201 includes a 1× mode voltage generation module 402 , a 1.5× mode voltage generation module 404 , and a 2× mode generation module 406 . The 1× mode voltage generation module 402 receives the battery input voltage V IN and generates an output voltage V OUT where V OUT =V IN . The 1× mode voltage generation module 402 requires a running clock signal (Clock) coupled to its CLK input in order to operate and generate the output voltage V OUT . The 1.5× mode voltage generation module 404 receives the battery input voltage V IN and generates an output voltage V OUT where V OUT =1.5×V IN . The 1.5× mode voltage generation module 404 also requires a running clock signal (Clock) coupled to its CLK input in order to operate and generate the output voltage V OUT . The 2× mode voltage generation module 406 receives the battery input voltage V IN and generates an output voltage V OUT where V OUT =2×V IN . The 2× mode voltage generation module 406 also requires a running clock signal (Clock) coupled to its CLK input in order to operate and generate the output voltage V OUT . The output voltage (V OUT ) of the charge pump 201 drives the LEDs 112 , 114 . The internal circuitry itself of the 1× mode voltage generation module 402 , 1.5× mode voltage generation module 404 , and 2× mode voltage generation module 406 are conventional and known in the art, and is not the subject of the invention disclosed herein.
[0039] A typical charge pump has 3 modes of operation as explained above, 1×, 1.5× and 2×. However, some LED applications may only need 1 mode of operation (1×) in the charge pump, in which case the charge pump 201 behaves as a low voltage dropout regulator. In other LED applications, all three operation modes may be needed in the charge pump 201 because the battery input voltage V IN can drop low enough and the voltage drop V LED across the LEDs 112 , 114 can be high enough. Thus, it would be very useful to activate or inactivate one or more of the 1× mode voltage generation module 402 , 1.5× mode voltage generation module 404 , 2× mode voltage generation module 406 in a convenient way.
[0040] The control data D 0 , D 1 , D 2 of the NVM 250 determines which one(s) of the 1× mode voltage generation module 402 , 1.5× mode voltage generation module 404 , 2× mode voltage generation module 406 becomes active. As shown in FIG. 4 , the control data D 0 , D 1 , D 2 are input to the AND gates 408 , 410 , 412 , respectively, to be AND'ed with the clock signal 270 . Thus, when D 0 =1, the signal 414 to the CLK input of the 1× mode voltage generation module 402 is the same as the clock signal 270 and thus the 1× mode voltage generation module 402 is active. But when D 0 =0, the signal 414 to the CLK input of the 1× mode voltage generation module 402 is inactive and thus the 1× mode voltage generation module 402 is inactive. When D 1 =1, the signal 416 to the CLK input of the 1.5× mode voltage generation module 404 is the same as the clock signal 270 and thus the 1.5× mode voltage generation module 404 is active. But when D 1 =0, the signal 416 to the CLK input of the 1.5× mode voltage generation module 404 is inactive and thus the 1.5× mode voltage generation module 404 is inactive. When D 2 =1, the signal 418 to the CLK input of the 2× mode voltage generation module 406 is the same as the clock signal 270 and thus the 2× mode voltage generation module 406 is active. But when D 2 =0, the signal 418 to the CLK input of the 2× mode voltage generation module 406 is inactive and thus the 2× mode voltage generation module 406 is inactive.
[0041] Therefore, activating or inactivating one or more of the operation modes of the charge pump 201 can be accomplished simply by programming the control data D 0 , D 1 , D 2 of the NVM 250 . If D 0 =1 but D 1 =0 and D 2 =0, the charge pump 201 is a single mode (1×) charge pump. However, if D 0 =D 1 =D 2 =1, the charge pump 201 becomes a tri-mode charge pump. Thus, there is no need to make 2 separate LED drivers with different mode charge pumps.
[0042] The present invention has the advantage that a variety of features, such as the LED current, internal resistance for setting the reference current for the LEDs, and the operation modes of the charge pump, may be conveniently set simply by programming the LED driver with the appropriate control data value in the NVM. Thus, an LED driver with different functionalities and features can be implemented as a single IC from the same die in the semiconductor fabrication process.
[0043] Upon reading this disclosure, those of skill in the art will appreciate still additional alternative structural and functional designs for a programmable LED driver. Thus, while particular embodiments and applications of the present invention have been illustrated and described, it is to be understood that the invention is not limited to the precise construction and components disclosed herein and that various modifications, changes and variations which will be apparent to those skilled in the art may be made in the arrangement, operation and details of the method and apparatus of the present invention disclosed herein without departing from the spirit and scope of the invention as defined in the appended claims.
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An LED driver includes an embedded non-volatile memory (NVM) capable of being programmed and storing control data for setting a variety of features of the LED driver, such as the maximum current for driving the LEDs, analog parameters such as the resistance of the internal resistor for setting the reference current for the LEDs, and the operation modes of the charge pump of the LED driver. This enables implementation of multiple LED driver product options without the need for different metallization steps during the fabrication process for the LED driver.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 62/003,304 filed May 27, 2014, and U.S. Provisional Application No. 62/126,007 filed Feb. 27, 2015. The disclosures of the above applications are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The invention relates generally to a latching valve assembly which has a latching mechanism that is able to hold a valve in an open position and a closed position, where the latching valve assembly is controlled by a circuit, and a change is detected in an electrical property of the circuit to identify the position of the latching mechanism, and therefore identify the position of the valve.
BACKGROUND OF THE INVENTION
[0003] There are many different types of valve assemblies, which are actuated by different methods. One type of valve assembly is used to control the flow of air and purge vapor between a fuel module of a fuel tank, and a carbon canister. Some types of valve assemblies include solenoids which control the position of some type of valve member, and are used to change the valve member between open and closed positions. It is often necessary to have some type of sensor device to detect the position of the valve member when the valve member is in the open position or the closed position. One example of an existing design approach is to use a mechanical sensing system through a reed switch, MR position sensor, mechanical switch or other position sensing either through contact or non contact methods. However, these types of solutions add more components, and increase cost.
[0004] Other types of approaches include using a pressure sensor in the fuel tank which determines position by monitoring pressure changes in the fuel tank as the valve assembly is changed between an open position and a closed position. However, this approach is not effective in applications which implement bleed flows in the valve assembly.
[0005] Accordingly, there exists a need for an approach to detect the position of a valve assembly which does not add unnecessary components, but is still effective in detecting the position of the valve assembly.
SUMMARY OF THE INVENTION
[0006] The present invention is a latching valve assembly which controls the flow of air and purge vapor between a fuel module and a carbon canister, where a change in an electrical property of the latching valve assembly is used to detect whether the latching valve is in the open position or the closed position. The latching valve assembly of the present invention eliminates the need for a physical switch solution, mechanical or non contact solutions, eliminates complexity of valve hardware requirements, and only adds minor electric components and software to identify the latch position. This system eliminates valve complexity and mechanical connections required for electrical conductivity.
[0007] In one embodiment, the present invention includes a valve portion controlled by a solenoid portion, where the valve portion latches in two positions, an open position and a closed position, and is held in either the open position or the closed position by a latching mechanism. The latching valve assembly uses two different portions of a coil to change the position of a valve assembly and detect the position of the valve assembly.
[0008] In each position, the armature is at rest at different locations within the solenoid. This results in a change in coil inductance that is electronically measured in one of the portions of the coil to identify the position of the valve portion when solenoid portion is inactive. With this embodiment, the position of the valve portion may be detected with one additional connector pin (using a ground common with the valve coil). This embodiment includes a separate coil wind that is used to enhance signal to noise ratio and part to part variation of inductance measurement.
[0009] In another embodiment, the present invention is a latching valve assembly which includes a solenoid portion having a magnet path, and a valve portion having an open position and a closed position, where the valve portion controlled by the solenoid portion. The valve assembly also includes a latching mechanism for maintaining the position of the valve position in the open position or the closed position when the solenoid portion is deactivated. A voltage pulse is emitted to the solenoid portion and used to detect whether the valve position is in the open position or the closed position. The voltage pulse is emitted over a time interval such that the latching mechanism and valve portion remain stationary, and is not long enough to actuate the latching mechanism or valve portion.
[0010] The solenoid portion includes an armature connected to the valve portion, and a coil substantially surrounding the armature, where the coil is also part of the solenoid portion. The armature is in a first position relative to the coil when the valve portion is in the closed position, and a second position relative to the coil when the valve portion is in the open position, such that different current measurements are produced when the armature is in the first position or the second position. The different current measurements correspond to whether the valve portion is in the open position or the closed position.
[0011] In an alternate embodiment, a magnet is disposed on the armature. The magnet is disposed in the magnet path when the valve portion is in the open position, and the magnet is out of the magnet path when the valve portion is in the closed position. The position of the valve assembly is detected by emitting more than one voltage pulse into the solenoid portion, and measuring the current generated by each voltage pulse. A different level of current is measured when the magnet is in the magnet path compared to when the magnet is out of the magnet path.
[0012] Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The present invention will become more fully understood from the detailed description and the accompanying drawings, wherein:
[0014] FIG. 1 is a perspective view of a latching valve assembly, according to embodiments of the present invention;
[0015] FIG. 2 is a sectional side view of a first embodiment of a latching valve assembly in an open position, according to embodiments of the present invention;
[0016] FIG. 3 is a sectional side view of a first embodiment of a latching valve assembly in a closed position, according to embodiments of the present invention;
[0017] FIG. 4 is a sectional side view of a second embodiment of a latching valve assembly in an open position, according to embodiments of the present invention;
[0018] FIG. 5 is a sectional side view of a second embodiment of a latching valve assembly changing between an open position and a closed position, according to embodiments of the present invention;
[0019] FIG. 6 is a sectional side view of a second embodiment of a latching valve assembly in a closed position, according to embodiments of the present invention;
[0020] FIG. 7 is a sectional side view of a third embodiment of a latching valve assembly in an open position, according to embodiments of the present invention;
[0021] FIG. 8 is a sectional side view of a third embodiment of a latching valve assembly changing between an open position and a closed position, according to embodiments of the present invention;
[0022] FIG. 9 is a sectional side view of a third embodiment of a latching valve assembly in a closed position, according to embodiments of the present invention;
[0023] FIG. 10 is a chart depicting the application of voltage to a coil to change the latching valve assembly between the open position and the closed position, and applying a voltage pulse before and after the latching valve assembly changes positions to obtain current measurements to detect the position of the latching valve assembly, according to embodiments of the present invention;
[0024] FIG. 11 is a chart depicting the application of voltage to a coil to change the latching valve assembly between the closed position and the open position, and applying a voltage pulse before and after the latching valve assembly changes positions to obtain current measurements to detect the position of the latching valve assembly, according to embodiments of the present invention; and
[0025] FIG. 12 is a chart depicting various current measurements taken during the operation of a third embodiment of a latching valve assembly, according to embodiments of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] The following description of the preferred embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
[0027] A latching valve assembly according to the present invention is shown in the Figures generally at 10 . The valve assembly 10 includes a solenoid portion, shown generally at 12 , and a valve portion, shown generally at 14 . The solenoid portion 12 operates to change the valve portion 14 between an open position, shown in FIG. 2 , and a closed position, shown in FIG. 3 .
[0028] The solenoid portion 12 includes an armature 16 connected to the valve portion 14 . Surrounding the armature 16 is a bobbin 18 , and surrounding the bobbin 18 is a coil 20 having a first portion 20 a and a second portion 20 b. Both portions 20 a, 20 b of the coil 20 are in electrical communication with a connector, shown generally at 22 . The connector 22 includes a plurality of terminals. More specifically, the connector 22 includes a first terminal, a second terminal, and a third terminal. The first terminal is in electrical communication with the both portions 20 a, 20 b of the coil 20 , the second terminal is in electrical communication with only the second portion 20 b of the coil 20 , and the third terminal is in electrical communication with only the first portion 20 a of the coil 20 .
[0029] The first portion 20 a of the coil 20 is has a resistance of around 20 Ohms, and the second portion 20 b of the coil 20 has a resistance of about less than 5 Ohms, but it is within the scope of the invention that other levels of resistance may be used.
[0030] When the valve portion 14 is in the closed position and the armature 16 is in a first position, as shown in FIG. 3 , and a current is applied to the first portion 20 a of the coil 20 using the first and third terminals, the armature 16 moves to a second position shown in FIG. 2 such that the valve portion 14 is in the open position. The valve portion 14 is held in the open position by a latching mechanism, shown generally at 24 , which has multiple positions. The latching mechanism 24 may be one similar to the latching mechanism described in U.S. application Ser. No. 14/487,448, the entire disclosure of which is incorporated herein by reference. One of the positions of the latching mechanism 24 functions to hold the valve portion 14 in the open position as shown in FIG. 2 , such that the coil 20 may be de-energized when the coil 20 is not being used to change the valve portion 14 between the open position and closed position.
[0031] The solenoid portion 12 is located in an overmold assembly 26 , where the overmold assembly 26 includes an overmold assembly cavity, shown generally at 28 , that is in fluid communication with a first port 30 , where the first port 30 is connected to and in fluid communication with a carbon canister. Connected to the overmold assembly 26 is a reservoir 32 having a reservoir cavity, shown generally at 34 . The valve portion 14 is partially disposed in the overmold assembly 26 and is adjacent the overmold assembly cavity 28 . A portion of the valve portion 14 is also partially disposed in the reservoir cavity 34 . Formed as part of the armature 16 is an extension rod 36 , which is part of the latching mechanism 24 . Connected to the extension rod 36 is a valve member, shown generally at 38 , which is selectively in contact with a valve seat 40 , where the valve seat 40 is formed as part of the reservoir 32 . Also formed as part of the reservoir 32 is a second port 42 , which is in fluid communication with the reservoir cavity 34 . The second port 42 is connected to and in fluid communication with a fuel module of a fuel tank. The valve member 38 includes a rigid core member 44 connected to the rod 36 , and a flexible stopper portion 46 connected to the core member 44 , and selectively in contact with the valve seat 40 .
[0032] There is also a stator insert 48 which is part of the solenoid portion 12 , and surrounded by the bobbin 18 . There is a gap 50 between the stator insert 48 and the armature 16 , where the gap 50 fluctuates in size, depending on whether or not the valve member 38 is in contact with the valve seat 40 , and the armature 16 is in the first position or second position.
[0033] To change the valve member 38 between open and closed positions, and the valve portion 14 is in the closed position, as shown in FIG. 3 , a current is applied to the first portion 20 a of the coil 20 , causing the armature 16 to move towards the stator insert 48 and the valve member 38 to move away from the valve seat 40 , decreasing the size of the gap 50 . The configuration of the latching mechanism 24 changes as the armature 16 moves relative to the latching mechanism 14 , regardless of whether the valve member 38 is in the open position of the closed position. Once the valve member 38 has moved far enough away from the valve seat 40 , the configuration of the latching mechanism 24 changes to maintain the valve member 38 in the open position, even when current is no longer applied to the coil 20 . The coil 20 is then de-energized, allowing the armature 16 and valve member 38 move a small amount away from the stator insert 48 , and be held in the open position because of the configuration of the latching mechanism 24 . Once the valve member 38 is in the open position and the armature 16 is in the second position, there is established fluid communication between the first port 30 and the second port 42 through the cavities 28 , 34 .
[0034] When it is desired to move the valve member 38 back to the closed position and the armature 16 back to the first position, a current is again applied to the first portion 20 a of the coil 20 , to move the armature 16 , rod 36 , and valve member 38 towards the stator insert 48 , reconfiguring the latching mechanism 24 such that when the current is no longer applied to the coil 20 , the armature 16 , rod 36 , and valve member 38 move towards and contact the valve seat 40 , placing the valve member 38 back in the closed position, as shown in FIG. 3 .
[0035] When the armature 16 is moved to change the valve portion 14 between the open position and closed position, there is a change in inductance in the second portion 20 b of the coil 20 , depending upon the position of the armature 16 relative to the coil 20 . A smaller gap 50 produces higher levels of inductance, and a larger gap 50 produces lower levels of inductance. There is one level of inductance measured when the armature 16 is in the position shown in FIG. 2 , and another level of inductance measured when the armature 16 is in the position shown in FIG. 3 . This change in inductance in the second portion 20 b of the coil 20 is measured through the first and second terminals. The change in inductance is measured by emitting a 12 Volt pulse through the second portion 20 b of the coil 20 . In one embodiment, the voltage pulse typically lasts between 5-15 milliseconds, and is therefore not long enough, or strong enough, to move the armature 16 , but is significant enough to cause a change in inductance in the coil 20 b that is measureable. It should be noted that it is within the scope of the invention that the voltage pulse used to detect the position of the valve portion 14 may last for longer or shorter time intervals, as long as the armature 16 and valve member 38 remain stationary. Because the change in inductance in the second portion 20 b of the coil 20 is measured, and the level of inductance change depends on the location of the armature 16 and corresponds to the location of the valve member 38 and the armature 16 , the location of the valve member 38 and the armature 16 is therefore detected and used to identify the position of the latching mechanism 24 .
[0036] A second embodiment of the present invention is shown in FIGS. 4-6 , with like numbers referring to like elements. In this embodiment, there is a magnet 52 mounted to the armature 16 , which moves into a magnet path 54 when the valve portion 14 is in the open position and the armature 16 is in the second position, shown in FIG. 4 , and moves out of the magnet path 54 when the valve portion 14 is in the closed position and the armature 16 is in the first position, shown in FIG. 6 . As with the previous embodiment, the latching mechanism 24 is able to maintain the position of the valve member 38 and the armature 16 in either the first position or the second position. The connector 22 of the latching valve assembly 10 in this embodiment only has two terminals, instead of three, as with the previous embodiment. Additionally, there is only one portion of the coil 20 a, instead of the coil 20 having a first portion 20 a and a second portion 20 b.
[0037] The operation of the latching valve assembly 10 is substantially the same as described in the previous embodiment, with one of the differences being the magnet 52 being attached to the armature 16 , and used for increasing the S/N ratio of the inductance measurement. In this embodiment, the inductance of the coil 20 is measured when the valve member 38 is in either the open position or the closed position, and is stationary (i.e., not transitioning between the open position and closed position as shown in FIG. 5 ). In this embodiment, a 12 Volt pulse is emitted through the coil 20 , and a measurement of the inductance of the coil 20 is then taken. The inductance of the coil 20 changes, depending upon whether the magnet 52 is located in the magnet path 54 , or the magnet 52 is not in the magnet path 54 . The presence of the magnet 52 in the magnet path 54 increases the signal-to-noise (S/N) ratio of the inductance measurement, whereas if the magnet 52 were not used, the S/N ratio would be insufficient, and the inductance would be difficult to measure. The magnet 52 essentially amplifies the inductance measurement when the valve member 38 is in the open position.
[0038] The voltage pulse lasts between 1-15 milliseconds, and is not long enough or strong enough to move the armature 16 , but is significant enough such that a change in inductance in the coil 20 is measureable. It should be noted that it is within the scope of the invention that the voltage pulse used to detect the position of the armature 16 and valve member 38 may last for longer or shorter time intervals, as long as the armature 16 and valve member 38 remain stationary. If the valve member 38 is in the open position, the armature 16 is in the second position, and the magnet 52 is in the magnet path 54 , the inductance of the coil 20 is at a certain level. If the valve member 38 is in the closed position, the armature 16 is in the first position, and the magnet 52 is not in the magnet path 54 , the inductance of the coil 20 is at a different level. The different levels of inductance correspond to the position of the valve member 38 and armature 16 . This change in inductance of the coil 20 is therefore used to determine whether the armature 16 and valve member 38 are in the open position or the closed position.
[0039] Another embodiment of the present invention is shown in FIGS. 7-12 , and has substantially the same structural configuration as the latching valve assembly 10 shown in FIGS. 4-6 , with the exception that the embodiment in FIGS. 7-12 does not have a magnet 52 . The solenoid portion 12 , the valve portion 14 , and the latching mechanism 24 work in substantially the same manner. However, the position of the armature 16 , and therefore the valve member 38 is detected by measuring current. The position of the valve portion 14 is able to be detected when the valve portion 14 is in either the open position, as shown in FIG. 7 , or the closed position, as shown in FIG. 9 . To detect the position of the valve member 38 and the armature 16 , a voltage pulse is sent across a sense resistor, and into the coil 20 of the solenoid portion 12 . The voltage pulse is not large enough or long enough to move the armature 16 , but creates a voltage across the sense resistor that is measured, which then corresponds to the current flowing through the sense resistor. It is within the scope of the invention that the voltage pulse used to detect the position of the valve portion 14 may last for any desired time interval, as long as the armature 16 and valve member 38 remain stationary. This value of the current varies depending on the location of the armature 16 , and valve member 38 , and therefore the position of the valve portion 14 . Although in this embodiment, a sense resistor is used to detect the position of the valve member 38 and armature 16 , it is within the scope of the invention that other electrical components in circuits having different configurations may be used.
[0040] Referring to FIG. 10 , a chart, shown generally at 70 , depicts the application of a voltage pulse to change the armature 16 and valve member 38 between the open position and the closed position, as well as the application of voltage pulses to detect the position of the armature 16 and the valve member 38 . There are two parameters plotted on the chart 70 , the first line 72 represents voltage, the second line 74 represents current. This chart 70 shows the voltage 72 at approximately zero up until approximately 1.25 milliseconds, at which point at a first voltage pulse 76 of about 15 Volts for 1.0 milliseconds is applied to the coil 20 , and a measurement of current is taken. As shown in FIG. 10 , the peak current taken during the 1.0 millisecond pulse was about 0.189 Amps. At about 1.38 milliseconds, a second voltage pulse 78 is applied to the coil 20 . This second voltage pulse 78 lasts about 150 milliseconds, but the current measurement is again taken at 1.0 millisecond of the second voltage pulse 78 , and as shown in FIG. 10 , the peak current measurement at 1.0 millisecond of the second voltage pulse 78 is about 0.179 Amps. The second voltage pulse 78 lasts a longer period of time, and functions to change the position of the valve potion 14 and the latching mechanism 24 . A third voltage pulse 80 is applied to the coil 20 at about 1.65 milliseconds. Similarly to the first voltage pulse 76 , the third voltage pulse 80 is about 1.0 milliseconds, and a third current measurement is taken at the peak current value during the third voltage pulse 80 . As shown in FIG. 10 , the peak current measured during the third voltage pulse 80 is about 0.274 Amps. The position of the armature 16 and valve member 38 is then determined by comparing the peak current measurements taken during the first voltage pulse 76 and the third voltage pulse 80 . As shown in FIG. 10 , the peak current measurement (0.189 Amps) taken during the first voltage pulse 76 is less than the peak current measurement (0.274 Amps) taken during the third voltage pulse 80 . The higher of the two current measurements indicates that the armature 16 and valve member 38 are in the closed position, and the lower of the two current measurements indicates that the armature 16 and valve member 38 are in the closed position. Therefore, when looking at FIG. 10 , armature 16 and the valve member 38 are initially in the open position, and then once the second voltage pulse 78 is applied to the coil 20 , the armature 16 and the valve member 38 are in the closed position.
[0041] Referring not to FIG. 11 , another chart, shown generally at 82 , depicts the application of a voltage pulse to change the armature 16 and valve member 38 between the closed position and the open position, as well as the application of voltage pulses to detect the position of the armature 16 and the valve member 38 . Both voltage 72 and current 74 are again depicted on the chart 82 . On this chart 82 , there are again three voltage pulses applied to the coil 20 , a fourth voltage pulse 84 , a fifth voltage pulse 86 , and a sixth voltage pulse 88 . The fifth voltage pulse 86 is used to change the position of the armature 16 and valve member 38 , and the current measurement is taken at about 1.0 milliseconds of the fifth voltage pulse 86 . The fourth voltage pulse 84 and sixth voltage pulse 88 are both about 1.0 millisecond, and are used to detect the position of the armature 16 and valve member 38 . Again the current measurements for the voltage pulses 84 , 88 are the peak current measurements. In FIG. 11 , it is shown that the peak current measurement taken during the fourth voltage pulse 84 is about 0.279 Amps, and the peak current measurement taken during the sixth voltage pulse 88 is about 0.183 Amps. The higher of the two current measurements indicates that the armature 16 and valve member 38 are in the closed position, and the lower of the two current measurements indicates that the armature 16 and valve member 38 are in the closed position. Therefore, when looking at FIG. 11 , armature 16 and the valve member 38 are initially in the closed position, and then once the fifth voltage pulse 86 is applied to the coil 20 , the armature 16 and the valve member 38 are in the open position.
[0042] Additionally, the voltage pulse being applied for different lengths of time produces different current measurements, which also depends on whether the valve member 38 is in the open position or closed position. Referring to FIG. 12 , there are several examples of current measurements taken at different time intervals, which are plotted on the chart 58 shown in FIG. 12 . The first of the current measurements are taken from a voltage pulse lasting 1.0 millisecond. The first measurements taken from the 1.0 millisecond pulse are shown at 60 a and 60 b, where the first curve 60 a represents a current measurement taken that corresponds to the armature 16 and valve member 38 being in the closed position, and the second curve 60 b represents a current measurement taken that corresponds to the armature 16 and valve member 38 being in the open position, and the magnet 52 is disposed in the magnet path 54 . It is shown in the chart 58 that the second curve 60 b has a greater peak than the first curve 60 a, and the difference between the peaks in the two curves 60 a, 60 b provides an indication of the position of the valve member 38 and armature 16 .
[0043] The third curve 62 a and fourth curve 62 b represent current measurements taken when a voltage pulse is applied for about 2.0 milliseconds. The fifth curve 64 a and sixth curve 64 b represent current measurements taken when a voltage pulse is applied for about 3.0 milliseconds. The seventh curve 66 a and eighth curve 66 b represent current measurements taken when a voltage pulse is applied for about 4.0 milliseconds. The ninth curve 68 a and tenth curve 68 b represent current measurements taken when a voltage pulse is applied for about 5.0 milliseconds. The peak of each curve 60 a, 60 b, 62 a, 62 b, 64 a, 64 b, 66 a, 66 b, 68 a, 68 b, represents the peak value, or RMS value, of the current at a set time, which in this embodiment is between 1.0 and 5.0 milliseconds, but it is within the scope of the invention that other time periods may be used. More specifically, the voltage pulse may be applied to the coil 20 for any length of time, as long as there is no movement of the valve member 28 and armature 16 .
[0044] It is also shown in the chart that the longer the voltage pulse, the greater amount of current is measured when the valve member 38 is in either of the open or closed positions. The current measurements taken at 1.0 millisecond are generally less than the current measurements taken at 2.0 milliseconds, the current measurements taken at 2.0 milliseconds are generally less than the current measurements taken at 3.0 milliseconds, the current measurements taken at 3.0 milliseconds are generally less than the current measurements taken at 4.0 milliseconds, and the current measurements taken at 4.0 milliseconds are generally less than the current measurements taken at 5.0 milliseconds.
[0045] However, the longer the voltage pulse, the greater the difference in the peak of each current measurement. For example, the difference between the peak of the first curve 60 a and the peak of the second curve 60 b is about 70 milliamps. When looking at the remaining curves on the chart 58 , it is shown that the difference between the peak of the third curve 62 a and the peak of the fourth curve 62 b is about 90 milliamps, the difference between the peak of the fifth curve 64 a and the peak of the sixth curve 64 b is 150 milliamps, the difference between the peak of the seventh curve 66 a and the peak of the eighth curve 66 b is 180 milliamps, and the difference between the peak of the ninth curve 68 a and the peak of the tenth curve 68 b is 290 milliamps.
[0046] One of the advantages of the present invention is that there is no need to change the construction of the valve assembly 10 . The current measurement, and therefore the position of the valve member 38 and armature 16 , is therefore detected by measuring the current in the coil 20 after applying the voltage pulse to the coil 20 for a specified time period. The specified time period of the voltage pulse may be any desired time period, as long as the valve member 28 and armature 16 remain stationary during the application of the voltage pulse. In yet another embodiment of the present invention, the magnet 52 may be attached to the armature 16 , and used for increasing the S/N ratio, and therefore improve the signal of the current measurement.
[0047] The description of the invention is merely exemplary in nature and, thus, variations that do not depart from the gist of the invention are intended to be within the scope of the invention. Such variations are not to be regarded as a departure from the spirit and scope of the invention.
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A latching valve assembly which controls the flow of air and purge vapor between a fuel module and a carbon canister, where a change in an electrical property of the latching valve assembly is used to detect whether the latching valve is in the open position or the closed position. The latching valve assembly of the present invention eliminates the need for a physical switch solution, mechanical or non contact solutions, eliminates complexity of valve hardware requirements, and only adds minor electric components and software to identify the latch position. This system eliminates valve complexity and mechanical connections required for electrical conductivity.
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This is a continuation of application Ser. No. 07/760,133 filed Sep. 16, 1991now abandoned.
FIELD OF THE INVENTION
The present invention relates to processes for preparing kraft pulp in which cellulosic material is treated with recycled pulping process liquids and fresh white liquor for dissolving the lignin therein. More particularly, the present invention relates to the recycling of spent cooking liquor from batch kraft cooking, and the advantageous reclamation of active dry solids and heat therein, while purging the harmful soap separating therefrom.
BACKGROUND OF THE INVENTION
In the kraft cooking process cellulosic material, most conveniently in form of chips, is treated at elevated temperatures with alkaline cooking liquor containing sodium hydroxide and sodium hydrogen sulfide. The fresh inorganic cooking liquor is referred to as white liquor, and the spent liquor containing the dissolved wood material is referred to as black liquor.
Since the initiation of kraft cooking processes to the present date, one of the most important objectives therein has been the attempt to reduce the energy consumption required to heat up the chips and chemicals. The method generally employed has been to recover heat energy at the end of the cooking process as it can then be used at the beginning of the process, as the chips and chemicals are brought together. In continuous cooking processes, this takes place by heating the chip material with secondary steam obtained from flashing the hot black liquor. In discontinuous, or batch cooking processes, however, the most useful technique is to use the recovered hot black liquor 1) as a direct heating media to be pumped into the digester and 2) to heat-up white liquor by means of heat exchangers.
In connection with this type of low-energy batch cooking, several methods for energy reclamation have been proposed. Some of these developments have resulted in industrial scale embodiments. Perhaps the most useful prior art method to date is that described in U.S. Pat. No. 4,578,149 by B. K. Fagerlund. This patent relates to an invention in which hot black liquor is displaced from the top of a batch digester to a particular hot black liquor accumulator by pumping wash filtrate into the bottom of the digester. This displacement into the accumulator is continued until the thermal displacement shows a clear drop in temperature after which the liquor is conducted to a separate tank for lower temperature black liquor. The reclamation of heat is then carried out by first pumping lower temperature black liquor into the next batch, and by then pumping hot black liquor from a hot black liquor accumulator, as well as hot white liquor warmed up by heat exchange with part of the hot black liquor into the batch. In this process the digester is brought up to a temperature approximately 20° C. below the final cooking temperature, thus providing for a major portion of the energy required in the form of fresh steam for heating the liquor in conventional batch cooking processes. In general, this technology can be classified as a "Two Tank" concept, i.e.--one black liquor accumulator for "hot" liquor and another one for "lower temperature" liquor.
The development of batch cooking technology has thus been characterized by improvements in terms of energy savings therein. Very little attention has been paid, however, to other important issues in cooking technology, such as the effect and variability of the properties of recovered black liquors, uniform cooking conditions, uniform pulp quality, and the sensitivity of these operations to disturbances therein. As an example, such a critical operational necessity as the removal of soap that separates from black liquors has not even been mentioned in the prior low-energy batch literature. The failure to consider these issues, however, has to a great extent been responsible for the tedious and troublesome start-ups of some low-energy batch digesters as well as operation in less than optimal conditions, which results in disturbances, production losses and variability in the degree of cooking and in pulp quality.
SUMMARY OF THE INVENTION
In accordance with the present invention, these and other objects have now been realized by the discovery of a method for discharging spent cooking liquor from a batch digester containing cooked lignocellulose-containing material in spent cooking liquor having a predetermined temperature and dry solids content, which method comprises supplying a first portion of a washing liquid to the digester in order to displace a first portion of the spent cooking liquor from the digester, the first portion of the spent cooking liquor having a temperature and dry solids content substantially corresponding to the predetermined temperature and dry solids content, supplying a second portion of washing liquid to the digester so as to displace a second portion of the spent cooking liquor from the digester, the second portion of spent cooking liquor having a temperature and dry solids content substantially lower than the predetermined temperature and dry solids content, and maintaining the first and second portions of spent cooking liquor separate from each other. In accordance with one embodiment of the method of the present invention, the predetermined temperature comprises the cooking temperature for the batch digester, and the temperature substantially lower than the predetermined temperature comprises a temperature corresponding to the boiling point of the cooking liquor at atmospheric pressure.
In accordance with one embodiment of the method of the present invention, the method includes monitoring the dry solids content of the spent cooking liquor in order to determine when the first portion of the spent cooking liquor has been obtained.
In accordance with another embodiment of the method of the present invention, the method includes monitoring the temperature of the spent cooking liquor in order to determine when the second portion of the spent cooking liquor has been obtained.
In accordance with yet another embodiment of the method of the present invention, the method includes employing the first portion of the spent cooking liquor as a heating liquor for cooking a subsequent batch of lignocellulose-containing material.
In another embodiment, the method of the present invention includes employing the second portion of the spent cooking liquor as a source of heat for heating liquor for cooking a subsequent batch of lignocellulose-containing material. In a preferred embodiment, this method includes transferring the second portion of the spent cooking liquor to a liquor tank maintained at atmospheric pressure.
In accordance with one embodiment of the method of the present invention, the method includes supplying a third portion of the washing liquid to the digester so as to displace a third portion of the spent cooking liquor from the digester, the third portion of the spent cooking liquor having a temperature lower than the temperature corresponding to the boiling point of the cooking liquor at atmospheric pressure.
In accordance with the present invention, a method has also been discovered for producing kraft pulp in a batch digesting process comprising charging lignocellulose-containing material to a batch digester, impregnating, pretreating and heating the lignocellulose-containing material by the addition of spent cooking liquor and/or fresh alkaline cooking liquor to the batch digester, cooking the lignocellulose-containing material at a predetermined cooking temperature so as to produce cooked lignocellulose-containing material having a predetermined temperature and dry solids content, discharging the spent cooking liquor from the batch digester by supplying a first portion of a washing liquid to the digester so as to displace a first portion of the spent cooking liquor from the digester, the first portion of the spent cooking liquor having a temperature and dry solids content substantially corresponding to the predetermined temperature and dry solids content, supplying a second portion of washing liquid to the digester so as to displace a second portion of the spent cooking liquor from the digester, the second portion of the spent cooking liquor having a temperature and dry solids content substantially lower than the predetermined temperature and dry solids content, maintaining the first and second portions of the spent cooking liquor separate from each other, utilizing the first portion of the spent cooking liquor for the pretreating and heating of the lignocellulose-containing material in a subsequent batch of lignocellulose-containing material, and utilizing the second portion of the spent cooking liquor for supplying heat to a subsequent batch of lignocellulose-containing material.
In a preferred embodiment of this method of the present invention, the method includes transferring the second portion of the spent cooking liquor, after supplying heat to the subsequent batch of lignocellulose-containing material, to a liquor tank maintained at atmospheric temperature. Preferably, this method includes separating and removing soap contained in the second portion of the spent cooking liquor in the liquor tank. More preferably, the liquor tank includes a primary compartment and a secondary compartment in liquid contact with each other, and the method includes transferring the second portion of the spent cooking liquor to the secondary compartment in the liquor tank. Most preferably, this method includes separating and removing soap from the second portion of the spent cooking liquor in the secondary compartment of the liquor tank.
In accordance with one embodiment of this method of the present invention, the method includes utilizing the second portion of the spent cooking liquor for impregnating the lignocellulose-containing material in a subsequent batch of lignocellulose-containing material. In a preferred embodiment, this method includes utilizing the second portion of the spent cooking liquor from the secondary compartment of the liquor tank for impregnating the lignocellulose-containing material in a subsequent batch of lignocellulose-containing material.
In accordance with another embodiment of this method of the present invention, the method includes utilizing the second portion of the spent cooking liquor for pre-heating fresh alkaline cooking liquor supplied to the digester in a subsequent batch of lignocellulose-containing material.
In another embodiment, this method includes supplying a third portion of washing liquid to the digester so as to displace a third portion of the spent cooking liquor from the digester, the third portion of the spent cooking liquor having a temperature lower than the temperature comprising the boiling point of the cooking liquor at atmospheric pressure. In a preferred embodiment, the washing liquid comprises a filtrate from a subsequent wash plant for kraft pulp.
In general, the present invention thus provides for overcoming the weaknesses in prior art low energy batch kraft cooking processes by means of a process for preparing kraft pulp which employs three tanks dedicated to particular black liquors, a new liquor recycling sequence, and the removal of soap at an optimum location in the process.
BRIEF DESCRIPTION OF THE DRAWINGS
In order to provide a proper description of the present invention and its comparison to the state of the art, it is crucial to understand exactly what happens in a terminal displacement of the kraft batch digester from the top of the digester by using wash filtrate pumped to the bottom of the digester. This understanding is more easily provided with reference to the following detailed description, which refers to the figures in which;
FIG. 1 is a graphical representation of the development of temperature and dry solids concentration in a displaced black liquor leaving the digester;
FIG. 2 is a graphical representation of the soap concentration during terminal displacement of the kraft batch digester as a function of pumped wash filtrate volume as the percentage of digester volume;
FIG. 3 is a graphical representation of residual alkali concentrations of hot black digester charges; and
FIG. 4 is a schematic representation of the tanks and liquor transfer sequences according to the method of the present invention.
FIG. 5 is a schematic representation of a kraft batch cooking process in accordance with the present invention.
DETAILED DESCRIPTION
Referring first to FIG. 1, this figure specifically shows the development of temperature and dry solids concentration of displaced black liquor leaving the digester. It is particularly important in order to understand the present invention to define different characteristic volume percentages describing different aspects of the volume of liquid filling the digester. Thus, and again referring to FIG. 1, Vtot, or digester total volume, means the total volume of the empty digester vessel; Vvoid, or digester free, or void volume, means the volume of the digester which is not filled by the chips; therefore, Vvoid=Vtot-Vchip volume. Vliq, or, digester liquid carrying capacity, means the sum of digester void liquid volume and liquid volume in chip material, or Vliq=Vtot-Vsolid phase.
In FIG. 1 the digester total volume, or Vtot, is marked to be 100%. In FIG. 1 the digester liquid-carrying capacity is Vtot minus the volume of the solid phase, or the fiber material, that is typically 90%. (The 90% liquid-carrying capacity value, i.e. all of the liquid in the digester, is derived from the fact that the final pulp consistency in a hydraulically full batch digester is about 10%, thus 90% being liquid.)
In FIG. 1 the digester void (free) volume, Vvoid, is the space not filled by chips, or is Vtot minus chip volume, and is typically 60%. (The 60% free liquid volume value is derived from the fact that softwood chips filling a batch digester typically fills about 160 kg of absolute dry wood solids per digester cubic meter. Furthermore, the specific density of softwood is about 0.4 kg per liter of wood material, thus providing a wood-filled space of about 0.4 m 3 per digester m 3 , therefore, 0.6 m 3 thereof is left for free liquid. Of course, this figure varies somewhat according to the degree of chip packing and with the specific density of the wood.)
When pumping colder wash filtrate, which is essentially at a temperature below the boiling point, or about 85° to 90° C., and having a dry solids content of 12%, to the bottom of the digester, the black liquor leaving from the top of the digester will have properties that differ according to the volume of filtrate pumped into the digester.
After pumping in about 60% of the Vtot the digester void volume is at a point where it is about to be completely replaced by the wash filtrate, which will subsequently start flowing out of the digester. This point (transition point 1) is seen in the "dry solids displacement curve" (DS) shown in FIG. 1, which then rapidly declines, tailing down towards the dry solids concentration of the wash filtrate, since the diffusion of dry solids from the internal volume of the chips to the void liquid is a slow process. The wash filtrate concentration level is first reached only after extended displacement volume, i.e.--at 130-140% of the digester total volume. However at transition point 1 the temperature of the liquor leaving the digester is still close to the cooking temperature, due to the rapid heat transfer which takes place from the internal volume of the chips, which includes an almost immobile liquid, to the moving liquor in the void volume.
After pumping in about 90% of the Vtot, the displaced volume equals approximately 100% of the liquid carrying capacity of the digester, and the internal chip heat content is almost totally conducted into the subsequently heated wash filtrate. This point (transition point 2) is seen in the "thermal displacement curve" (TEMP) shown in FIG. 1 which declines rapidly, tailing down towards the temperature of the wash filtrate.
FIG. 2 shows the behavior of soap concentration during terminal displacement of the kraft batch digester as a function of the volume of pumped wash filtrate as a percentage of digester Vtot. It is important to note the opposite development of soap concentration, which is due to the fact that the wash filtrate has a higher soap concentration, i.e.--about 8 g/l, than that of the black liquor at the end of the cook, i.e.--about 2 g/l, and which therefore results in the soap concentration of the liquor leaving the digester starting to increase at transition point 1, when the wash filtrate starts to break through. As the portion of the wash filtrate increases, as displacement proceeds, this concentration then approaches that of the wash filtrate.
According to the prior art, as in U.S. Pat. No. 4,578,149, for example, the displaced liquor is recovered to the hot black liquor accumulator according to the thermal displacement, i.e.--the cut-off to the lower temperature accumulator is determined according to transition point 2. This procedure evidently efficiently recovers the heat, but fails to maintain constant black liquor quality. As the displacement proceeds over 60% of Vtot, the dry solids curve drops sharply. When approaching 90% of displaced volume, the dry solids concentration has decreased close to that of the wash filtrate. As a consequence, the concentration of useful cooking chemicals, and especially residual alkali and sulphur, is very low at the end of the recovery of the hot black liquor. This diluted liquor, however, enters the hot black liquor accumulator, and as the hot black liquor is used for following cooks, black liquor of varying chemical composition will be charged. Consequently, the cooking conditions will vary therein, causing unavoidable variations in the degree of cooking and in the pulp quality. Also, large amounts of undesirable soap are simultaneously recovered in the hot black liquor accumulator.
FIG. 3 illustrates residual alkali concentrations as measured from hit black liquor charges entering an industrial kraft batch digester in a digester house operated according to the process described in U.S. Pat. No. 4,578,149. It is evident therefrom that the residual alkali concentration varies randomly between about 10 and 17 g of Effective Alkali per liter, precisely as FIG. 1 would anticipate, i.e.--the dry solids concentration can vary between about 12.5 and 21%.
Referring next to FIG. 4, the tanks and liquor transfer sequence of the present invention are illustrated. According to the invention, at the end of a kraft batch cook, the terminal displacement of digester liquor by pumping wash filtrate E to the bottom of the digester is first carried out to the first transition point (see FIG. 1) removing essentially all of the rich spent liquor at cooking temperature and pressure from the free liquid volume. This displaced liquor is digested as B1 and is transferred to the black liquor tank 1, at point B. The exact volume to be recovered is most suitably controlled by monitoring the dry solids concentration in the displaced liquor exiting from digester top with conventional dry solids analyzers. After detecting a clear drop in dry solids concentration, the displaced liquor is switched to enter black liquor tank 2 until a temperature close to the atmospheric boiling point thereof is reached. This displaced liquor is referred to as D1 and is thus recovered. This end point is clearly farther than the transition point 2 (see FIG. 1), which corresponds to the displacement volume at which the heat content of the liquid-carrying capacity volume is being recovered in the displacing wash filtrate, meaning that a complete heat recovery has taken place. In order to further wash the pulp, the pumping of wash filtrate can then be continued, and the corresponding displaced liquor A1 is led to the atmospheric black liquor tank 3, at point AB.
It is noteworthy that when proceeding in this manner, the first black liquor portion, B1, is both 1) essentially at cooking temperature and 2) at the dry solids concentration at the cooking end point. No prior art technology is able to fulfill these two important requirements for purity in a single liquor located in a dedicated tank. On the other hand, the second recovered black liquor, D1, contains diluting wash filtrate which starts to break through at the transition point 1. It is important to note that black liquor, D1, is of varying black liquor quality, and also contains most of the soap since the soap concentration, see FIG. 2, first increases when the filtrate is breaking through into the black liquor after transition point 1. No prior art technology is able to recover a single portion of black liquor in a dedicated tank that contains all of the variability in dry solids content and temperature, and a selectively higher soap concentration. The mixed liquor in black liquor tank 2 is used solely to heat up white liquor and warm water in heat exchangers, and to then end up in black liquor tank 3, compartment S, to be further used as impregnation black liquor AA.
The black liquor tank 3, and its compartment S, now have a significant new role in kraft cooking. That is, the function of receiving compartment S is to remove the separating soap from the cooled and depressurized black liquor from black liquor tank 2, and to isolate the low-in-soap black liquor for impregnation purposes. Compartment S is connected to the main reservoir of the black liquor tank 3 by a pipe that extends from near the bottom thereof in order to prevent the soap from entering the other side or compartment thereof. No prior art technology is able to separate soap from the recovered black liquor and to selectively feed the low-in-soap black liquor back into the process. Practical experience in industrial processes has proven that soap removal in this location of the black liquor transfer sequence is of major importance. Technology such as that described in U.S. Pat. No. 4,579,149 does not even recognize the soap problem, and clearly provides no solution for dealing therewith. In addition, this type of two tank heat recovery concept must, by its very nature, be pressurized, which therefore effectively prevents one from removing the separated soap therefrom. As a consequence, the prior art technology is hampered by repeated operational problems, when the accumulated soap in the black liquor tanks slowly gets transferred to the digester, causing severe problem in maintaining digester circulation, and in preventing efficient liquid displacement operations.
According to the present invention, and as illustrated in FIG. 5, the kraft batch cook is instituted by filling the digester with chips, filling the digester and soaking the chips with low-in-soap black liquor AA from receiving compartment S in black liquor tank, 3, in order to fully impregnate the chip material with black liquor. The use of an overflow, A2, back to black liquor tank 3, at point AB, is preferred, in order to remove air and the first diluted material. During impregnation, a rather low temperature, below the boiling point, is preferred, since higher temperature impregnation will consume the residual alkali too fast, thus causing impregnation with zero residual alkali black liquor, in turn resulting in higher rejects and non-uniform cooking. This, in fact, is another advantageous feature of the present invention, since the black liquor AA is inherently at the desired temperature, contrary to prior art technologies which feed in black liquor for impregnating at temperatures well above the boiling point.
The black liquor impregnation step is terminated by pressurizing the digester in order to avoid flashing during the following steps, that introduce higher temperature liquors. According to the present invention, the kraft cooking process is then continued by pumping in hot black liquor, B, from black liquor tank 1. In contrast to the prior art, black liquor from tank 1 is of constant temperature and dry solids concentration, which makes it easy to repeat exactly the same hot black liquor charge from cook to cook. This is extremely important because the hot black liquor step has a major chemical effect on the wood, and controls the selectivity and cooking kinetics in the main cooking phase with white liquor. In the prior art, the effect of hot black liquor has been neglected, and a good portion of the reaction degree and variability in pulp quality can be related to the uncontrolled properties of the black liquor quality.
Therefore, in the case of low-energy, displaced kraft batch cooking, it is particularly beneficial to combine the present invention with a novel kraft cooking method as set forth in U.S. Pat. No. 5,183,535, the disclosure of which is incorporated herein by reference thereto, taking advantage of a well controlled black liquor treatment in terms of more effective cooking and improved pulp quality.
The cooler black liquor, A3, which has been displaced by hot black liquor is conducted to black liquor tank 3, at point AB, for discharge to the evaporation plant and for the recovery of cooking chemicals.
The cooking sequence is continued by pumping in hot white liquor from the hot white liquor storage tank, C, and a smaller amount of hot black liquor, B, 1) simultaneously with the hot white liquor, in order to recover as much heat as possible, and to dilute the very high alkali concentration of fresh white liquor and 2) after white liquor charge, in order to flush the lines into the digester. The total volume of hot black liquor, B, consumed in this sequence corresponds to the volume of the recovered hot black liquor, B1, from the previous batch. The displaced liquor, D2, above about atmospheric boiling point, is conducted to hot black liquor tank 2.
After the above-described filling procedure, the digester temperature is relatively close to the final cooking temperature. The final heating up is carried out in conventional manner by using direct or indirect heating. After cooking reactions have proceeded to the desired reaction degree, the batch is ready to be displaced with wash filtrate E as described at the beginning of this description. The sequence can then repeat itself.
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.
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Methods for discharging spent cooking liquors from a batch digester containing cooked lignocellulose-containing material in spent cooking liquor are disclosed, including supplying a first portion of washing liquid to the digester to displace a first portion of the spent cooking liquor at a temperature and dry solids content which substantially corresponds to the temperature and dry solids content of the spent cooking liquor at the end of the batch digestion, supplying a second portion of washing liquid to the digester to displace a second portion of the spent cooking liquor having a temperature and dry solids content substantially lower than that of the spent cooking liquor in the digester, and maintaining the first and second portions of spent cooking liquor separate from each other. Methods of producing kraft pulp in batch digesting processes using this method are also disclosed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a National Phase Entry of International Application No. PCT/IB2011/054463, filed on Oct. 10, 2011, which claims priority to French Patent Application Serial No. 1058250, filed on Oct. 11, 2010, both of which are incorporated by reference herein.
TECHNICAL FIELD
[0002] The invention relates to a unit (of the column type) for establishing contact between a liquid and a gas, particularly suitable for use on a floating platform. The aim is to limit the effects of the movement of the floating platform on the effectiveness of the gas-liquid contact. The invention particularly applies to washing natural gas using a basic solution so as to extract the acid compounds (carbon dioxide and hydrogen sulfide) therefrom. It also applies to drying gas by contact between the gas and a hygroscopic liquid such as triethylene glycol (TEG) or diethylene glycol (DEG), as well as columns for regenerating those liquids. It may also be applied to hydrocarbon distillation.
BACKGROUND
[0003] Offshore hydrocarbon exploitation leads to the use of various treatment methods on oil platforms. However, when the sea is too deep, it is not possible to use stationary platforms, and floating platforms, often called FPSO (Floating Production Storage and Off-loading), are used. These floating platforms are subject to the movements of the sea, which they transmit to the equipment they bear. Among these, the columns, whether distillation or absorber columns, are among the most sensitive to movement. In fact, the effectiveness of this equipment depends on the quality of the contact between the descending liquid and the vapor that rises in the columns.
[0004] The most traditional method for establishing good contact between the liquid and vapor consists of forcing the gas to pass through ports formed in a tray on which the liquid flows. However, in such tray columns, the quality of the contact between the liquid and vapor depends on the horizontally of the trays; any angle relative to the horizontal, even a small one, can lead to dry a part of the tray from liquid, which then no longer ensures contact between the liquid and vapor. For that reason, operators of plants on floating platforms prefer random or structured packing over trays. Document FR 2777533 describes a floating maritime structure having a structured packing with a particular geometry designed to reduce the impact of the marine oscillations on the operation of the structure.
[0005] Random packing consists of metal or ceramic pieces that are positioned so as to fill the entire cross-section of the column, in a disordered manner. The complex shape ensures good contact between the liquid and the vapor. Structured packing consists of plates shaped and arranged together so as to ensure the passage of the gas and liquid with good contact.
[0006] FIG. 1 shows a traditional column arrangement equipped with packing. The configuration is similar for disordered packing and structured packing. The column here comprises two packing beds A and B. They are sprayed with liquid using distributors C and D that ensure the distribution thereof on the entire cross-section of the column. A collector E collects the liquid from the bed A; the liquid is then distributed by the distributor D on the bed B. The proper operation of the packing assumes that the liquid is regularly distributed over the entire cross-section of the column so as to avoid dry areas, which would cause part of the rising vapor not to be in contact with the liquid.
[0007] In traditional liquid distributors, the liquid coming from the top of the column arrives in a chute, the bottom of which is pierced with holes. Each of these holes is across from a secondary chute that it feeds with liquid. The secondary chutes, the bottoms of which are in turn pierced with distribution holes, ensure uniform spraying of the cross-section of the column.
[0008] Furthermore, in traditional liquid distributors, the chutes are open at the apex and the liquid level established inside is also subject to the movements of the FPSO. As a result, depending on the incline, the distribution holes are covered by a higher or lower liquid level. Since the flow rate through each hole depends on the liquid height submerging it, the flow rates are therefore not identical, which leads to irregular spraying of the cross-section of the column. Certain distribution ports may not be submerged in the liquid, which leads to dry areas in the packing. The liquid/vapor contact quality is therefore affected.
[0009] Document US 2008/0271983 proposes to modify the liquid distributor so as to ensure a regular distribution of the liquid over the entire cross-section of the column, irrespective of the incline. An illustration thereof is provided in FIG. 2 , taken from that document.
[0010] The liquid is distributed on the cross-section of the column using primary 32 and secondary 33 chutes which, unlike traditional distributors, are closed. Each primary chute 32 is supplied by a vertical tube 31 . The chutes are pierced on the lower surface thereof with ports that ensure the distribution of the liquid, whereof the diameter is calculated such that the liquid level is established relatively high in the vertical tube 31 . Thus, the pressure differences that may appear at the perpendicular to each of the ports due to the incline of the column become negligible faced with the hydrostatic height produced by the liquid level in the vertical tube 31 . A uniform distribution of the liquid may thus be ensured over the entire cross-section of the column. These distributors are described as pressure distributors.
[0011] However, the main drawback of this device lies in the height of liquid that is necessary in the vertical tube 31 . In fact, for the device to be effective, this height must be significantly greater than the height variations between the different parts of the chutes that result from the incline of the column. The height of the vertical tube 31 therefore commonly reaches 3 to 4 m.
[0012] Furthermore, when the column is inclined, the liquid tends, within the packing, to accumulate on the side toward which the column is tilted, until it may encounter the shell on which it flows without returning toward the inside of the packing. The uniformity of the liquid distribution obtained using the pressurized distributor is thus broken. In order to avoid this harmful effect, it is necessary to collect the liquid and redistribute it approximately every 4 to 5 m so as to eliminate the edge effects.
[0013] As a result of the above, the height of a column following the model of that described in document US 2008/0271983 is significantly greater than a standard column, with an equal flow rate. This results in bulk and weight constraints that are difficult to reconcile with the constraints of a tight environment, such as that of floating platforms. Consequently, there is a need to design a new unit for establishing contact between a gas and a liquid that is capable of operating effectively on a floating platform despite the movements thereof, and having smaller sizes than the units of the state of the art.
SUMMARY
[0014] The invention first relates to a unit for establishing contact between a liquid and a gas, comprising:
a chamber having a vertical axis; a first series of contact sections positioned along the length of the vertical axis of the chamber; a second series of contact sections positioned along the length of the vertical axis of the chamber, alternated with the contact sections of the first series; a liquid circulation system adapted for circulating a liquid in the contact sections of the first series and in the contact sections of the second series in a separate manner.
[0019] According to one embodiment, each contact section comprises a liquid distribution system, a liquid collection system, and packing positioned between the liquid distribution system and the liquid collection system. According to one embodiment, the packing is of the structured or random type. According to one embodiment, the unit comprises connecting ducts adapted for conveying the liquid between the successive contact sections of the first series on the one hand, and between the successive contact sections of the second series on the other hand.
[0020] According to one embodiment, the connecting ducts between the contact sections of the first series pass through the contact sections of the second series; and the connecting ducts between the contact sections of the second series pass through the contact sections of the first series. According to one embodiment, the connecting ducts are at least partially arranged outside the chamber. According to one embodiment, the unit comprises:
a first liquid intake duct feeding a contact section of the first series; a second liquid intake duct feeding a contact section of the second series; liquid collection means at a lower end of the chamber.
According to one embodiment, the unit comprises:
a single gas intake duct at a lower end of the chamber; a single gas collection duct at an upper end of the chamber.
According to one embodiment, the unit is a distillation unit or a drying unit for a gaseous mixture or a deacidification unit for a gaseous mixture, and preferably is a hydrocarbon distillation unit or a natural gas drying unit or a natural gas deacidification unit.
[0026] The invention also relates to a method for establishing contact between a liquid and a gas, comprising feeding a unit as described above with gas and liquid, and optionally collecting gas and liquid coming from the unit. According to one embodiment, this method is a method for deacidifying a gaseous mixture, in which the gas feeding the unit is preferably natural gas and the liquid feeding the unit is a basic solution, preferably comprising an amine compound. According to another embodiment, this method is a method for drying a gaseous mixture, in which the gas feeding the unit is preferably natural gas and the liquid feeding the unit is a hygroscopic liquid, preferably comprising a glycol compound. According to another embodiment, this method is a hydrocarbon distillation method. According to one embodiment, this method is implemented offshore using a floating platform.
[0027] The present invention makes it possible to overcome the drawbacks of the state of the art. It more particularly provides a unit for establishing contact between a gas and a liquid capable of working effectively on a floating platform (despite the movements thereof) and which may be smaller than the devices of the state of the art (and in particular those described in document US 2008/0271983). This is accomplished owing to an alternating arrangement of packing beds and distributors feeding them, so as to use the entire available volume of the column.
BRIEF DESCRIPTION OF THE FIGURES
[0028] FIG. 1 diagrammatically shows a traditional packing contactor (state of the art).
[0029] FIG. 2 diagrammatically shows a detail of a contactor for a floating platform according to the state of the art (document US 2008/0271983).
[0030] FIG. 3 diagrammatically shows one embodiment of a unit according to the invention.
[0031] FIG. 4 diagrammatically shows another embodiment of the unit according to the invention.
[0032] FIG. 5 diagrammatically shows a natural gas deacidification unit.
DETAILED DESCRIPTION
[0033] The invention is now described in more detail and non-limitingly in the following description. A first embodiment is illustrated in FIG. 3 . This embodiment preferably relates to a wash column with a solution with a base of an amine compound, to purify acid gases (primarily carbon dioxide and hydrogen sulfide) contained in natural gas. Preferably, the column is a countercurrent column.
[0034] The column comprises a chamber 20 (or shell) defining a vertical axis. For example, the chamber 20 may be essentially cylindrical. The natural gas to be treated feeds the column at the base thereof through a gas intake duct 1 . The liquid (lean or regenerated amine solution) is introduced at the head of the column through a first liquid intake duct 2 and a second liquid intake duct 3 . The flow rate of each of these feeds is reduced by approximately half relative to the single feed used in the state of the art. The purified gas is recovered at the apex of the column by a gas collection duct 4 .
[0035] Contact sections 5 , 6 , 7 , 8 are positioned along the vertical axis of the column. Each contact section 5 , 6 , 7 , 8 is adapted for promoting contact between the gas and the liquid, and therefore comprises a packing bed 14 , 15 (which may be a structured or random packing). A distinction is made between a first series of contact sections 5 , 7 and a second series of contact sections 6 , 8 , the two series being positioned alternating. Thus, any contact section adjacent to a contact section of the first series belongs to the second series; and likewise, any contact section adjacent to a contact section of the second series belongs to the first series.
[0036] In the illustrated example, from the head of the column toward the base, are successively arranged: a first contact section 5 of the first series, a first contact section 6 of the second series, a second contact section 7 of the first series, and lastly a second contact section 8 of the second series. The total number of contact sections maybe even or odd. There are at least three contact sections in all (in which case, one of the series comprises only one contact section, surrounded by two contact sections of the other series). Advantageously, the total number of contact sections may be set at 4 or 5.
[0037] The liquid is distributed at the head of each contact section 5 , 6 , 7 , 8 by a liquid distribution system 9 , 12 , and collected at the base of each contact section 5 , 6 by a liquid collection system 11 , 18 . The unit is provided such that the liquid circulates separately (or independently) in the column on the one hand in the contact sections 5 , 7 of the first series, and on the other hand in the contact sections 6 , 8 of the second series. Connecting ducts 10 , 13 allow circulation of the liquid between two successive contact sections within each series. In other words, there is no exchange of liquid between the first series and the second series.
[0038] More specifically, in the illustrated situation, the first liquid intake duct 2 feeds the distribution system 9 of the first contact section 5 of the first series. At the base of that contact section 5 , the amine solution is collected in the collection system 11 of the first contact section 5 of the first series, it is conveyed in the first connecting duct 10 of the first series, and it feeds the distribution system of the second contact section 7 of the first series. The same means are repeated similarly if the first series includes a third contact section or several successive contact sections.
[0039] Likewise, still in the illustrated situation, the second liquid intake duct 3 feeds the distribution system 12 of the first contact section 6 of the second series. At the base of that contact section 6 , the amine solution is collected in the collection system 18 of the first contact section 6 of the second series, it is conveyed in the first connecting duct 13 of the second series, and it feeds the distribution system of the second contact section 8 of the second series. The same means are repeated similarly if the second series includes a third contact section or several successive contact sections.
[0040] The assembly consisting of a connecting duct and a distribution system that it feeds is advantageously similar to the liquid distribution equipment described above relative to FIG. 2 , and which is described in more detail in document US 2008/0271983. In particular, advantageously, the connecting duct is a tube or hose closed over its entire circumference, and the liquid distribution system comprises a set of hoses whereof the entire circumference is closed, with the exception only of ports designed for liquid to exit toward the packing (and connections between hoses).
[0041] With the arrangement described above, the liquid between the first contact section 5 of the first series and the second contact section 7 of the first series (just as, in the illustrated case, between the first contact section 6 of the second series and the second contact section 8 of the second series) does not go through the packing bed of the contact section 6 ( 7 , respectively) situated between those contact sections. In this way, it is possible both to:
avoid any loss of space in the unit, by minimizing spaces not occupied by packing and which are therefore not dedicated to liquid/gas contact strictly speaking; and benefit from a sufficient hydrostatic pressure in each distribution system (owing to the connecting ducts) to prevent any distribution heterogeneity with the overall movements of the unit.
[0044] The vertical dimension of the connecting ducts 10 , 13 is adapted such that the height differences that may appear between the ends of the distribution systems 9 , 12 when the column is inclined are negligible relative to said vertical dimension of the connecting ducts 10 , 13 . For example, the connecting ducts may have a dimension larger than 1 m, or 2 m, or 3 m, or 4 m, in the vertical direction; and/or may be adapted to contain a volume of liquid having a dimension in the vertical direction greater than or equal to 1 m, or 2 m, or 3 m, or 4 m. It therefore appears that the unit according to the invention allows a uniform feeding of the packing beds using pressurized distributors positioned alternating with the packing beds.
[0045] At the base of the column, the amine solution from the two series of contact sections 5 , 6 , 7 , 8 can be recovered in a single liquid collection duct 17 . The amine solution is then sent to a regeneration device. The single liquid collection duct 17 is supplied on the one hand with liquid coming directly from the contact section situated closest to the base (in the illustrated case, this is the second contact section 8 of the second series), and on the other hand by the liquid from the immediately adjacent contact section (in the illustrated case, this is the second contact section 7 of the first series), which is recovered using a last connecting duct 16 .
[0046] According to another embodiment not shown, the amine solution from the first series of contact sections 5 , 7 is recovered at the base of the column by a first liquid collection duct, while the amine solution from the second series of contact sections 6 , 8 is recovered at the base of the column by a second liquid collection duct. The amine solutions recovered in these two liquid collection ducts have different purities. There is therefore an energy gain if they are introduced into the regeneration device separately at different levels. This embodiment assumes the presence of one flash drum by liquid collection duct. It is thus possible to partially offset the increased vapor consumption related to the increase of the amine solution flow rate.
[0047] Still in reference to FIG. 3 , each connecting duct 10 , 13 , 16 (between the successive contact sections within each series, and at the output of the next-to-last contact section of the column) passes through the following contact section (i.e., the adjacent contact section, at the base of the contact section from which it came). When two connecting ducts are present on the same altitude of the column (for example, the connecting ducts 10 , 13 between the collection system 18 of the first contact section 6 of the second series and the distribution system of the second contact section 7 of the first series), the design of the distribution and collection systems may be such that these connecting ducts are coaxial to the center of the column.
[0048] According to another embodiment shown in FIG. 4 (where the references bear the same meaning as above), each connecting duct 10 , 13 , 16 bypasses the following contact section, for example by being positioned at least partially outside the chamber 20 . The embodiment of FIG. 3 makes it possible to use traditional chambers and is therefore more practical in terms of boilers working and tubing. Conversely, the embodiment of FIG. 4 makes it possible to use traditional packing beds and to preserve a maximal cross-section for the packing.
[0049] It is possible to provide a feed using two amine solutions with different purities (in the respective liquid intake ducts 2 , 3 ), which is advantageous if one wishes to perform a relatively shallow purification of the gas. This unit has been described for an absorption column with an amine solution, but it is also possible to provide any other type of column, for example a gas-glycol contactor for drying the gas, a condensate stabilization column, or a distillation column. If applicable, the unit is provided with additional means so as to be able to perform the appropriate function, for example heating means and/or cooling means.
EXAMPLE
[0050] In the following example, the aim is to extract the carbon dioxide contained in natural gas. The composition of the natural gas is as follows:
[0000] COMPONENT MOLAR % Carbon dioxide 10.04 Nitrogen 0.03 Water 0.14 Methane 81.69 Ethane 5.53 Propane 1.65 i-butane 0.28 n-butane 0.31 Pentane + 0.47
The content to be achieved at the head of the column for the purified gas is 50 ppm vol of carbon dioxide in the gas. The natural gas flow rate at the inlet of the column is 19626 kmol/h.
[0051] FIG. 5 diagrammatically shows an extraction unit for extracting acid gas from the natural gas. The natural gas containing acid gas 1 ′ enters the absorber A. It is washed therein at countercurrent by the regenerated amine solution, which is introduced in 2 ′. The purified gas exits in 3 ′. The amine solution charged with acid gases leaves the absorber in 4 ′, and is expanded and degassed in the extraction drum BF. It is then heated from 6 ′ to 7 ′, then enters the regeneration column R. It exits purified of acid gases in 16 ′, is successively cooled from 16 ′ to 18 ′, pumped by the pumps P 1 and P 2 up to the pressure of the absorber A, and the cycle begins again.
[0052] In FIG. 5 , the feeding of the absorber with the amine solution is done only at the head, according to the state of the art. The distributors are those pressurized distributors described in document US 2008/0271983, with a hydrostatic height of approximately 4 m. The flow rate of the amine solution 2 ′ is 1048 t/h.
[0053] If the absorber A is now replaced with the unit according to the invention, the flow rate of amine solution 2 ′ is divided into two identical portions that feed the absorber A separately (through the ducts 2 and 3 of FIG. 3 or 4 ). Subsequently, the gas is treated in the intermediate contact section 6 using a purer solution than in the configuration of the state of the art, but the final purity in the upper contact section 5 is only ensured by a portion of the flow rate. As a result, these two factors act at counter purposes, and the total flow rate is increased up to 1415 t/h, or 707.5 t/h for each of the feeds.
[0054] The corollary to the increase in the total amine solution flow rate is an increase in the size of the regeneration equipment (the flash drum BF and the regeneration column R). However, the impact of this size increase on the total weight of the amine wash unit remains limited, as the regeneration equipment operates at low pressure.
[0055] However, the diameter of absorber is most often determined by the liquid solution flow rate that descends along the column. Since the amine flow rate is divided in two, it follows that each bed is only passed through by 707.5 t/h instead of 1048 t/h in the case of the state of the art. The diameter of the high-pressure absorber is thus reduced. Lastly, using the volume left empty by the distributor of the state of the art makes it possible to decrease the height of the absorber.
[0056] The dimensions and weights of the equipment are summarized in the tables below:
State of the art:
[0057]
[0000]
Diameter (mm)
Height (mm)
Weight (t)
Absorber
3400
41100
729
Flash drum
3200
9700
55
Regenerator
4400
26500
268
Invention:
[0058]
[0000]
Diameter (mm)
Height (mm)
Weight (t)
Absorber
3100
34000
504
Flash drum
3500
10500
73
Regenerator
4700
26500
303
[0059] The invention therefore shows a total mass gain of 172 t. However, the mass gain on the absorber, which is the heaviest and most difficult piece of equipment to install, is 225 t. This results in a more balanced distribution of the masses between the various modules of the floating platform and easier production of the assembly. Furthermore, the mass gains are calculated relative to the treatment equipment alone. They do not include the structure supporting them, the mass of which is approximately twice that of the equipment. The total gain is therefore approximately 700 t for the module bearing the absorber and 500 t for the amine wash unit assembly, given the increase in the mass of the regeneration equipment.
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A unit for establishing contact between a liquid and a gas includes: a chamber having a vertical axis; a first series of contact sections disposed along the length of the vertical axis of the chamber; a second series of contact sections disposed along the length of the vertical axis of the chamber, alternated with the contact sections of the first series; and a liquid circulation system designed to circulate a liquid in the contact sections of the first series and in the contact sections of the second series in a separate manner.
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FIELD OF THE INVENTION
The present invention relates to fail-safe equipment for monitoring flames in fire boxes of boilers, incinerators, and the like. More particularly, it relates to the detection and fail-safe amplification of signals from a flame monitoring photo-detector, without the use of a mechanical shutter.
BACKGROUND OF THE INVENTION
The conventional way to provide fail-safe flame monitoring is to employ a mechanical shutter which interrupts the passage of light from the flame to a photocell at a predetermined rate of interruption. In this way, a "flame-on" condition will be indicated only by signals from the photocell occurring at the predetermined rate. Any other response from the photocell will indicate either a "flame out" condition or an equipment failure, and, in order to be safe, the burner system will be shut down to determine what the problem is. This is what is meant by the term "fail-safe".
Mechanical shutters, however, have numerous drawbacks. They have a motor drive and moving parts, which can give trouble. The bearings also are a problem, especially in the portions nearest the flame where the heat is greatest and lubrication is difficult. They take up space, they are labor-intensive, and, therefore, expensive to install. All of these factors contribute to their high initial cost and high cost of maintenance. It is, therefore, a general objective of this invention to provide a flame monitoring equipment, which is fail-safe but which eliminates the mechanical shutter.
Another problem encountered in modern flame monitoring, is the detection of flames in the presence of smoke, pulverized coal, dirt, ash or other adverse condition which may be associated with the flame in a fire-box. In this connection, a high degree of sensitivity is desireable along with full fail-safeness. Accordingly, the provision of high sensitivity together with full fail-safeness is a further object of the invention.
BRIEF DESCRIPTION OF THE INVENTION
In the accomplishments of these and other objects of the invention, in a preferred embodiment thereof, a photovoltaic light detector (silicon diode) is employed to generate a signal in response to light impinging upon it. When that light comes directly from the axial mid-portion of a flame, the intensity of the light will vary according to a "flicker frequency" and, therefore, the signal from the detector has the flicker frequency superimposed on it. The signal is then amplified by a circuit which responds extremely rapidly and applies maximum amplification to all signals up to a given value. Above that value the amplification is gradually reduced so as to avoid saturation of the amplifier. The reduction of amplification is accomplished by a feedback circuit which establishes a maximum amplification for the peak amplitude of the signals from the detector (including flicker). In this way, all frequencies down to D.C. (including flicker frequency as well as D.C.) are amplified equally. The signals are then processed further downstream in order to isolate the flicker frequencies for the purpose of indicating a "flame-on" condition in the conventional manner.
It is a feature of the invention that the signals from the detector are switched on and off by means of a switch located between the detector and the amplifier, which is operated by a timer designed, in a preferred embodiment to close the switch for 800 m/sec (milliseconds) every second. This provides an interrupted signal from the detector which is virtually the same as that provided by conventional shutters and provides complete self-checking for all components in the system but for the photodetector which, being photovoltaic, can only fail in a non-conducting mode. Thus, the system is rendered "fail-safe" without the use of a mechanical shutter.
It is a feature of the invention that the presence or absence of a flicker frequency in the output provides additional self-checking.
Still another feature of the invention is that the rapidity of the response and the maximum amplification of all signals up to the given value, assures maximum sensitivity and permits the detection of low intensity and "dirty" flames.
A further feature in one embodiment of the invention relates to interrupting the signal from the detector by means of a variable resistance whereby the signal is applied gradually to the amplifier so as to avoid saturation of the amplifier which otherwise results from the instantaneous application of the full flame signal to the amplifier.
Further objects and features will be understood from the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
The preferred embodiments herein shown are depicted in the accompanying drawings in which:
FIG. 1 is a schematic of the circuit of the invention showing switches for providing self-checking, and
FIG. 2 is a schematic of the circuit of the invention showing a variable resistance form of switch.
DETAILED DESCRIPTION OF THE INVENTION
A preferred embodiment of the invention comprises a silicon diode photovoltaic light detector D1 appropriately arranged in the conventional manner in an optical system (not shown) to view along the center axis of a flame so as to provide flicker frequencies when a flame is present. D1 generates a current whenever light strikes it, the value of the current being proportional to the intensity of the light.
The circuit comprises the outputs of the photo detector D1 applied via a FET Analog Switch S1 to the input terminals of a FET Input Operational Amplifier U1. The output of U1 is connected directly to a capacitor C3 (0.047 uf) which provides an AC output for the system. A feedback network for controlling the amplification of U1, comprises an R/C combination R1 (330k) and C1 (100 pf), and an N-channel J FET (J Field Effect Transistor) Q1 in series with a resistor R2 (1k); with the RC combination, and Q1, R2 combination connected respectively in parallel between the output and the negative input of U1. The feedback network is controlled by a low voltage varistor V1, which is connected between the output of U1 and the center tap of a voltage divider R3 (1 meg), R4 (1 meg) and ground. The center tap of the voltage divider also is connected through FET Analog Switch S2 to the gate of Q1. A capacitor C2 (4.7 uf) is also connected between the gate of Q1 and ground.
Switches S1 and S2 are indicated by the dotted lines in FIG. 1 designated 10 and comprise dual FET Analog simultaneously acting switches. They are controlled by a timer, not shown, to be closed for 800 m/second opened for 200 m/sec to simulate the operation of a conventional mechanical shutter. The on-off period is a matter of choice. The only reason 800 m/s-200 m/s is chosen here is that such timing is required in West Germany.
When the switches S1, S2 are closed, signals from D1 are amplified by U1 at full amplification until an output peak voltage of U1 of about +3 volts is reached, at which point V1 commences conducting, and the voltage at the gate of Q1 rises (becomes more positive) causing Q1 to conduct and thereby reduce the amplification of Q1. The resistance of V1 drops increasingly as the output voltage of U1 rises, thereby causing the negative feedback to prevent peak amplification by U1 greater than about 8 volts. When the signal from D-1 diminishes, however, the resistance of V1 very rapidly increases proportionally and capacitor C2 causes the voltage at the gate of Q1 to remain substantially constant. When switch S2 opens, the charge on C2 remains unchanged, but when switch S2 is closed, the charge on C2 gradually diminishes (becomes more negative) when the output of U1 is low. In this way. the amplification of U1 is controlled by the peak value of the signals from D1, and all frequencies down to DC are amplified equally. The AC output at C3, therefore, contains all frequencies detected by D1, equally amplified. The "flicker" frequencies which indicate a flame-on condition, are separated from the very low frequencies by conventional filtering components further downstream.
The circuit is extremely sensitive because it has no minimum threshold. It amplifies and transmits downstream all detectable signals. Its extremely rapid response also protects U1 from heavy saturation from transients of more than about 500 u/sec duration. The periodic switching of S1 provides full self-checking throughout the system, and since D1 is photovoltaic, it can only fail in the off mode. Thus, the system is completely fail-safe.
In the embodiment of FIG. 2, an LED/CdS photocoupler is employed as a switch indicated within the dotted lines 20. A timer operates the photocoupler 20 through an inverting amplifier U2 and current limiting resistor R5. The photocoupler acts as a variable resistance with a gradual rise from an "off" condition to an "on" condition within approximately 50 m/s. The advantage of this is to apply the signal from D1 to U1 gradually and, thereby to avoid the saturation (and consequent ringing) of U1, which the quick closure of S1 (or of a mechanical shutter) causes. This provides an increase in the useful period of flame observation, and, thereby, increasing the efficiency of the system.
The time constant established by C2 and R3, R4 is such that the highest peak signal from D1 over a substantial period controls the amplification of U1, and in the circuit shown, if the signals at D1 cease,the amplification of U1 will not regain maximum amplification for about 500 m/sec (milliseconds). This period, however, can be varied depending upon conditions. Thus, if a quicker return to high sensitivity is desired, the recovery rate can be shortened by decreasing the value of C2. On the other hand, it is important for the operation of the circuit that the negative feedback network limit the amplification of U1 in response to the peak value of signals from D1 over a substantial period of, at least, about 100 m/sec so as to allow equal amplification of virtually all frequencies.
In view of the preferred embodiments herein described, those skilled in the art will now recognize that variations can be made without departing from the spirit of the invention, and, therefore, it is not intended to confine the invention to the precise form herein shown but rather to limit it solely in terms of the appended claims.
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A fail-safe, self-checking flame monitoring circuit is provided without the use of a mechanical shutter in which a photodetector provides a signal corresponding to flame intensity (including flicker), an amplifier amplifies the signal, the amplification is controlled by a negative feedback circuit in relation to the peak amplitude of the signal (including flicker) such that all frequencies down to DC are amplified equally, and all amplified signals are passed, without threshold, downstream for further processing.
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COPYRIGHT MATERIAL
The disclosure of this patent contains material which is the subject of copyright protection. Reproduction of the patent document as it appears in the Patent and Trademark Office is permitted in furtherance of the United States Patent Laws (Title 35 United States Code). The copyright owner reserves all other rights under the United States Copyright Laws (Title 17 United States Code).
CROSS-REFERENCE TO RELATED APPLICATIONS
The invention described and claimed herein is related to U.S. patent application Ser. Nos. 07/867,422 and 07/867,423 which were both filed Apr. 13, 1992 and assigned to the same assignee herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention is an optical correlator system having reflective optical components positioned along an asymmetrically folded optical axis or path between an electromagnetic radiation beam generator, which can be a laser that generates a beam of coherent light, and an output light detector for recognition of information processed along the optical path by active ones of the reflective optical components.
2. Description of the Related Art
Optical correlators can perform complex pattern recognition more rapidly than known digital techniques. Optical correlators are capable of processing large amounts of data in a data stream that can be useful in the detection, extraction and classification of desired information included in the data. Although known optical systems can perform extremely high speed, two-dimensional pattern recognition, their development has been hindered by the lack of suitable optical components; particularly at the input plane and at the spatial filter plane. However, the recent development of magneto-optic display assemblies (for example, see William E. Ross' U.S. Pat. No. 4,550,983, which is assigned to the same assignee) now provide a two-dimensional array of electronically programmable light shutters or valves that can be used to enter information into optical correlators at very high rates, e.g., at this time about 2000 frames per second. Such optical correlators can operate in, or nearly at, real-time. [See Mills and Ross, "Dynamic Magneto-optic Correlator: Real-time Operation", Society of Photo-Optical Instrumentation Engineers (SPIE) Acoustic-Optic, Electro-Optic and Magneto-Optic Devices and Applications (1987) vol. 753, pp 54-63.]
U.S. Pat. No. 5,148,496 by Robert H. Anderson, similarly assigned, teaches a discoid optical correlator system having reflective optical components positioned along a symmetrically folded optical axis or path between a source of light and an output light detector.
The discoid optical correlator system of Patent '496 has the folded optical path developed within a special disk. By definition, the disk is circular in shape and its perimeter or rim is regular. As a circle, its diameter D is the root in any determination of a folded optical path which is composed of one or more path segments (D, 2D,..nD). Therefore, each segment has a length determined by D, and each is of equal length as taught by this Patent. Also, the total length of the optical path and the number of its path segments in a folded configuration within the discoid is limited by its regular circumference or perimeter. This further determines the number of optical correlator components that can be positioned along the optical path.
The '496 Patent also teaches that the optical components are either active or passive. Its active optical components, excluding the laser diode and the charge coupled detector (CCD) array, are the input spatial light modulator (SLM) chip and the filter SLM chip. The passive components are the several concave and plane mirrors. These active and passive components are positioned along the symmetrical optical path between the laser diode and the CCD detector array in a sequence dictated by the disk diameter D which interposes passive optical components to link the active components. In the '496 Patent, the linear optical correlator path which is symmetrically folded within the discoid structure does not sequentially alternate and interpose the passive optical components in a desired active-passive-active-passive arrangement between a source of electromagnetic radiation and a detector array.
OBJECTS OF THE INVENTION
Accordingly, it is an object of the invention to provide a new improved optical correlator system having a folded asymmetrical axis or path.
It is an object of the invention to provide an optical correlator system having a folded asymmetrical optical path including unequal path segments.
It is an object of the invention to provide an optical correlator system that is able to withstand extreme environments such as wide temperature ranges and severe vibration levels.
It is an object of the invention to provide an optical correlator system that is able to withstand extreme acceleration and shock forces.
It is an object of the invention to provide an optical correlator system resistant to imposed centrifugal force.
It is an object of the invention to provide an optical correlator system having reflective optical components, both active and passive, arranged in an asymmetrical and folded optical path.
It is an object of the invention to provide a relatively small and lightweight optical correlator system with improved mechanical rigidity in various operating environments.
SUMMARY OF THE INVENTION
Briefly, in accordance with the invention, an optical correlator system is disclosed having a plurality of reflective optical components, a source of electromagnetic radiation, such as visible light, and an output detector which are positioned around an asymmetrical perimeter region of a planar body to develop an asymmetrical and folded or zigzag optical axis or path traversed by the beam of electromagnetic radiation so that an unknown object is optically detected which is then subject to a process of identification.
While the specification concludes with claims particularly pointing out and distinctly claiming the subject matter which may be regarded as the invention, the organization and method of operation, together with further objects, features, and the attending advantages thereof, may best be understood when the following description is read in connection with the accompanying drawing(s).
BRIEF DESCRIPTION OF THE DRAWING(S)
FIG. 1 is a perspective view of the optical correlator system with its asymmetrical reflective optical components as a preferred embodiment of the invention.
FIG. 2 is a plan view of a longitudinal cross section of a planar support body for the optical correlator system of FIG. 1.
FIG. 3 is a longitudinal cross section of the optical correlator system of FIG. 1.
FIG. 4 is a schematic of a PRIOR ART VanderLugt linear optical correlator system.
FIG. 5 is a graphical representation of an output waveform of an optical correlator system such as that of FIG. 1 and of FIG. 4.
DESCRIPTION OF THE INVENTION
Referring to FIG. 1, a preferred embodiment of the reflective optical correlator system 10 of the present invention includes a planar support body 12 having an asymmetrical or irregular perimeter 14 with a plurality of system stations 16 formed at selected locations along the irregular perimeter of the support body. Respective ones of a plurality of reflective optical components 18, both active and passive, are positioned at selected and associated ones of the system stations. An electromagnetic radiation source 20 positioned at a system alpha station generates, for example, a coherent light beam which traverses a folded asymmetrical optical axis or path 22 developed within the planar body 12 and bounded or defined by the reflective optical components 18. The optical path 22 terminates at an array detector 24 positioned at a system omega station.
Referring now to FIGS. 2 and 3, the planar body 12 of the extremely compact reflective optical correlator system 10 of the invention is preferably formed from a Zerodur™ material which maintains all of the passive and active optical components in a fixed and stable configuration with respect to each other over various hostile environments such as vibration and temperature variations. Zerodur is a glass ceramic with the lowest temperature expansion coefficient of any presently known material (7×10 -8 per °Centigrade) which provides maximum positional stability of all the active and passive components of the optical correlator system 10 relative to each other. Coupled with its excellent mechanical rigidity, Zerodur also has excellent machining and polishing properties.
As shown particularly by FIGS. 2 and 3, the asymmetrical folded or zigzag optical path 22 is formed by a series of ports or tunnels bored into and through the Zerodur material to provide a clear or material free optical path. Optical path 22 removes any degradation associated with the index-of-refraction changes, if any, of the Zerodur block 12. Such changes as caused by material inhomogeneities or temperature fluctuations would translate directly into intensity and phase changes across the beam and, hence, cause degradation. Furthermore, the clear optical path 22 eliminates interfaces between the optical block 12 and the active and passive components as listed above. Reflections from such interfaces could create interference with a light beam traversing the tunnel path 22, and distort its information bearing content as will be described. It is contemplated that in certain optical correlator systems, the clear optical path 22 could be evacuated and filled with an inert gas, such as helium, at a partial pressure to eliminate contaminants from the optical path, and to prevent possible chemical corrosion of the active and passive components.
The correlator body 12 can also be formed from a transparent, fused quartz (SiO 2 ). Because natural quartz which is birefringent can cause problems when used with a coherent or polarized light beam, fused quartz is considered to be preferred. It is contemplated that other materials such as glass, acrylic or similar clear plastic compositions could also be considered for use in forming the correlator support body 12.
The asymmetrical and folded optical path 22 that is formed within the Zerodur body 12 has several sequential path segments 22a through 22e as shown in particular by FIG. 2. As can be seen in FIG. 2, it is evident that the length of a path segment can be different from another path segment; for example, the length of path segment 22e is less than the length of path segment 22d. The length of path segment 22e is accurately determined by the size of the output correlator pattern traversing the optical path; in particular, from the last reflective component 18 to "paint" the array detector 24 so that its physical detector plane surface is maximized to record the output pattern. Yet it is also apparent that certain of the path segments, such as segments 22b and 22c, can have the same length. The asymmetry of the optical path and its total path length (the sum of the lengths of the individual segments) is determined by the required distances between the active and passive optical components. For the optical correlator system 10 of the invention, these sequentially joined path segments of selected same or differing lengths develop the folded, asymmetrical optical path 22.
The description herein of the optical correlator system 10 of the invention with its asymmetrical and zigzag folded optical path 22 should be considered and understood in view of a PRIOR ART VanderLugt linear optical correlator system 30 as shown by FIG. 4. A PRIOR ART VanderLugt linear optical correlator system is taught in greater detail by U.S. Pat. No. 5,148,496. This PRIOR ART linear optical correlator system 30 as shown by FIG. 4 has a laser 32 that develops a high intensity output beam 34 which is collimated through a collimator 36, and then expanded and focused by a suitable lens system onto an input spatial light modulator (SLM) 38. This input SLM 38 has a transmission function f(x,y) which represents an object to be identified. Lens 40 images the Fourier transform of f(x,y), F(u,v) onto a filter SLM 42 in the Fourier plane. The filter SLM 42 has a transmission function H(u,v), where H(u,v) is the Fourier transform of some function h(x,y). The optical field immediately downstream after the filter SLM 42 then is the product of F(u,v)H(u,v). A second lens 44 images the Fourier transform of this product onto a detector 46, and auto-correlation produces a bright spot in its detector plane.
The distance d from the filter SLM chip 42 to lens 44 is not critical to the operation of the PRIOR ART linear optical correlator system 30 of FIG. 4 since it affects neither the correlation intensity pattern nor the imaging condition from the input plane at SLM chip 38 to the detector plane at detector 46. Therefore, to detect and identify an object, its transmission function f(x,y) is correlated against a set of filters H l (u,v) . . . H n (u,v). Each of these filters is written onto the filter plane SLM 42 sequentially, and the correlation for each is obtained. The filter produces an auto-correlation peak, such as peak 50 of FIG. 5, at the detector plane of detector 46 that indicates the location of the object and permits its identification.
Accordingly, the optical correlator system 10 of the invention as shown by FIGS. 1 through 3 depends on the folding of a linear optical axis or path, like that of the above PRIOR ART linear optical correlator system 30 of FIG. 4, into the asymmetrical and zigzag folded optical path 22 as shown.
Referring now to FIG. 3, the reflective optical correlator system 10 of the invention includes both active and passive optical components or elements as follows:
1. Active elements:
electromagnetic radiation source 20,
input spatial light modulator (SLM) 52,
filter SLM 54, and
array detector 24.
2. Passive elements:
planar support body 12,
reflective toric mirrors 56 and 58,
unit 60 that includes (1) a collimator, which is an assembly of several lenses, and (2) a Gaussian intensity filter; and, polarizers 64, 66 and 68.
The electromagnetic radiation source 20 of coherent visible light is a conventional diode laser positioned at the alpha station of the optical correlator system 10. One visible diode laser has a 685 mm wavelength with an optical output power of 20 mW. Such a laser develops a high intensity output beam that is collimated and filtered by unit 60. The collimator portion of unit 60 corrects for astigmatism and output beam ellipticity, and produces a round, collimated beam; here, the beam exits the unit 60 with an approximate 6 mm Gaussian diameter. Since the input SLM 52 is preferably illuminated by a plane wave with uniform intensity, a Gaussian intensity filter portion of unit 60 cooperates with the collimator portion. The filter has a Gaussian absorption profile so that the exiting filtered beam has an intensity which is uniform over 6 mm.
The input SLM 52 is an electrically addressable magneto-optic chip that operates in a reflective mode. One such magneto-optic SLM or MOSLM™ chip is the subject of the above listed related applications. These MOSLM chips are available from the Data Systems Division of Litton Systems, Inc., Agoura Hills, Calif. This input SLM 52 is a MOSLM chip having a 128×128 pixel array with pixel-to-pixel spacing of 24 microns (22 microns pixels with a 2 micron gap between pixels that are organized in rows and columns; the active area is a square measuring 3.1 mm on a side).
The filter SLM 54 is structurally identical to but functionally different from the input SLM 52.
Three polarizers 64, 66 and 68 are used in the optical path 22 of the optical correlator system 10 of the invention. These polarizers are made of a dichroic film coated onto the surface of an optical flat. Each has a high extinction ratio (for example, 2000:1) and a high parallel transmission coefficient (for example, over 80 percent). Since each of the SLM chips 52 and 54 has an array of pixels which, in accordance with the Faraday effect, selectively rotate incoming linearly polarized light, then each SLM chip requires an entrance polarizer and an exit polarizer which functions as an analyzer. Polarizer 64 is positioned in the optical path 22 between the collimator-filter unit 60 and the input SLM 52 to affect the exiting collimated and filtered beam exiting from the unit 60. The second polarizer 66 is positioned to intercept the light beam traversing the optical path 22 as it passes to and is reflected from toric mirror 56. The polarizer 66 functions as the input SLM 52 exit analyzer, and correspondingly as the filter SLM 54 entrance polarizer. Polarizer 68 is positioned just prior to the array detector 24.
As passive components or elements, mirrors 56 and 58 function to produce the first and second Fourier transforms. Since astigmatism is a concern in such optical systems for Fourier transforms, the mirror surfaces are not spherical in the optical correlator system 10 of the invention. The concave mirror surface of each mirror 56 and 58 is toric. By definition, a toric mirror has a segment of an equilateral zone of a torus which results in different refracting power in different meridians. That is, each toric mirror has two radii of curvature where the radius of curvature with respect to the meridional plane differs from that along the sagittal plane; here in the optical correlator system 10 this difference is about two percent (2%). These toric surfaces take into account the incidence angle of the optical beam, and correct for optical aberrations that would be produced if the mirror surface were a spherical surface illuminated at this incidence angle. Stated another way, the toric correction depends on the particular incidence angle.
In the optical correlator system 10 of the invention as shown by FIG. 3, the focal length of mirror 56 is determined by
f.sub.1 =N.sub.f P.sub.f P.sub.i /λn (1)
where N f =128 which is determined by the use of a 128×128 input SLM 52 and a 128×128 filter SLM 54 with pixel spacing P i =24 microns and P f =24 microns, respectively. Lambda is equal to the laser wavelength, and n is equal to the refractive index of the medium with air=1. The focal length f 2 of mirror 58 is determined by the desired magnification of the system.
In one optical correlator system 10 of the invention, the selected magnification for the system is 2/3 which matches the correlation size of the particular array detector 24. Therefore, in this system, f 2 =2/3 f 1 where f 1 =107.7 mm, and f 2 =71.75 mm. Using a predetermined 8° incidence angle in this system, then the radii of curvature for the toric mirrors 56 and 58 are:
Mirror 56: R m =215.26, R s =219.54
Mirror 58 R m =143.51, R s =146.36
where subscript s=Sagittal (the plane of FIG. 3), and subscript m=Meidional (the plane perpendicular to the plane of FIG. 3).
The toric mirrors 56 and 58 used in the optical correlator system 10 of the invention as shown by FIG. 3 can be fabricated from high quality mirror substrate materials such as Zerodur glass. Zerodur substrates are highly polishable and exhibit very low thermal expansion; both important qualities for mirror substrates. Dielectric coatings can be used for high reflection and durability.
Continuing with the optical correlator system 10, the array detector 24 in the preferred embodiment of the system is a charge coupled device (CCD) positioned at the optical correlator output plane detector or omega station as a frame transfer device. In the optical correlator system 10 as described above, the CCD detector 24 has a 128×128 pixel array. Again, this pixel array is oriented in rows and columns like the pixel array of input SLM 52 and filter SLM 54. However, the CCD detector pixel array has a 16 micron pixel size and a 4 mm 2 active imaging area. The planar surface of the CCD detector 24 is positioned parallel to the plane defined by the planar reflective surfaces of the input SLM 52 and the filter SLM 54. It is contemplated that in certain operational systems, the CCD detector could be positioned at an angle equal to a predetermined angle as measured in degrees from the axis of the optical path as determined by the sphericity of the preceding toric mirror. This would permit the optical beam reflected by the toric mirror to "paint the best picture" on the pixel array of the CCD detector 24.
The linear distance of optical path segment 22e (see FIG. 2) between the toric mirror 58 and the CCD array 24 as has been described is determined by the comparative difference between the 24 micron pixel size for both pixel arrays of the input SLM 52 and the filter SLM 54, and the 16 micron pixel size of the pixel array for CCD detector 24. Although the length of path segment 20a is different than that of path segment 20e, it is contemplated that there will be embodiments of the optical correlator system 10 of the invention where these path segments could be of equal or nearly equal length. Lastly, in this embodiment of the optical correlator system 10 of the invention, the CCD array 24 has a 3000:1 dynamic range, although this is not considered to be critical to the operation of the system, and a 6 MHz output data rate.
Relative positional stability of the active and passive components attached to the planar support body 12 is a key factor in proper optical correlator operation. Why? because the most severe requirement of the optical correlator system 10 is the faithful mapping of the information content of the optical beam from an input pixel on the input SLM 42 onto the corresponding filter pixel on the filter SLM 54. For this primary reason then, the seal utilized for the active and passive components must ensure the positional stability of all the components with respect to the Zerodur planar support body 12. This has primary importance particularly under operating environments having a wide range of temperatures and vibration levels; as well as those of extreme acceleration and shock imposed forces. In one embodiment, rigid mounting of the active components is accomplished through the use of alumina (Al 2 O 3 ) for the input SLM 52 and filter SLM 54, and Kovar (a registered trademark) for the CCD array 24. This maximizes the seal positional stability and reliability without an adverse affect on the magnetic field associated with each MOSLM SLM. The passive components can be either formed in place or attached to the Zerodur block using epoxy or similar organic adhesives or materials.
As will be evidenced from the foregoing description, certain aspects of the invention are not limited to the particular details of construction as illustrated, and it is contemplated that other modification and applications will occur to these skilled in the art. It is, therefore, intended that the appended claims shall cover such modifications and applications that do not depart from the true spirit and scope of the invention.
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An optical correlator system having a plurality of reflective optical components, both active and passive, positioned (1) between a source of electromagnetic radiation, such as a visible beam of coherent light, and an output detector array, and (2) around an asymmetrical perimeter of a planar support body to develop an asymmetrically folded optical axis or path wholly within the body where the path is traversed by the beam SO THAT information processed by the active optical components along the optical path and imparted to the optical beam enable the optical detection of an unknown object at the detector array which is then subject to an identification process.
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CROSS-REFERENCE TO RELATED APPLICATION
This application claims under 35 U.S.C. §119(a) the benefit of Korean Patent Application No. 10-2011-0097846 filed on Sep. 27, 2011, the entire contents of which are incorporated herein by reference.
BACKGROUND
(a) Technical Field
The present invention relates to compositions and methods for manufacturing a cathode for a secondary battery. More particularly, the present invention relates to compositions and methods for manufacturing a cathode for a secondary battery, where the cathode includes manganese fluorophosphate with lithium or sodium.
(b) Background Art
As the use of portable small-sized electronic devices has become widespread, there has been an active interest in developing new types of secondary batteries such as, for example, nickel metal hydrogen or lithium secondary batteries. For example, a lithium secondary battery uses carbon (such as, e.g., graphite) as an anode composition, lithium-containing oxide as a cathode composition, and a non-aqueous solvent as an electrolyte. Lithium is a metal that has a very high tendency to undergo ionization; consequently, lithium can achieve a high voltage. Thus, lithium is often used in the development of batteries having high energy density.
In a lithium battery, a cathode composition typically includes a lithium transition metal oxide containing lithium in which 90% or greater of the lithium transition metal oxide includes layered lithium transition metal oxides (such as, e.g., cobalt-based, nickel-based, cobalt/nickel/manganese ternary-based, and the like). However, when such layered lithium transition metal oxides are used as a cathode composition, lattice oxygen within the layered lithium transition metal oxides may become deintercalated and participate in an undesired reaction under non-ideal conditions (such as, e.g., overcharge and high temperature), thereby causing the battery to catch fire or explode.
In order to overcome the disadvantages of such layered lithium transition metal oxides, researchers have considered cathode compositions having a spinel or olivine structure. In particular, it has been suggested that a cathode composition including a spinel-based lithium manganese oxide having a three dimensional lithium movement path, or a polyanion-based lithium metal phosphate having an olivine structure, instead of a layered lithium transition metal oxide, may prevent problems in lithium secondary batteries that arise from decreased stability in layered lithium transition metal oxides as a result of cathode deterioration.
The use of the spinel-based lithium manganese oxide as a cathode material has been limited because repeated cycles of battery charging and discharging results in lithium elution. Moreover, spinel-based lithium manganese oxide containing compositions display structural instability as a result of the Jahn-Teller distortion effect.
The use of olivine-based lithium metal phosphates, such as iron (Fe)-based phosphate and manganese (Mn)-based phosphate, as a cathode material has also been limited because these compounds have low electrical conductivity. However, through the use of nano-sized particles and carbon coating, the problem of low electrical conductivity has been improved, and thus the use of olivine-based lithium metal phosphates as a cathode composition has become possible.
For example, it has been recently reported that fluorophosphates may be useful as a cathode material. The fluorophosphate has the following formula: A 2 MPO 4 F, where A represents Li or Na, and M represents a transition metal such as Mn, Fe, Co, Ni, V, or a mixture thereof. Theoretically, the fluorophosphate of formula A 2 MPO 4 F is expected to have a capacity about twice as high as a conventional lithium metal phosphate since it has two Na atoms. For example, in the case where a fluorophosphate having the formula Na 2 MPO 4 F (M=Mn, Fe, Co, Ni, V or a mixture thereof) is used as a cathode material for a lithium secondary battery, sodium is deintercalated during the initial charging step and lithium is intercalated during the initial discharging step. In the following cycles of battery charging and discharging, alternating intercalation and deintercalation of lithium occurs during the charging and discharging process. Similarly, in the case where Na 2 MPO 4 F (M=Mn, Fe, Co, Ni, V or a mixture thereof) is used as a cathode material for a sodium battery, the intercalation and deintercalation of sodium is carried out during charging and discharging.
U.S. Pat. No. 6,872,492 discloses an example of using a fluorophosphate including sodium, such as NaVPO 4 F, Na 2 FePO 4 F, or (Na,Li) 2 FePO 4 F, as a cathode material for a sodium based battery. However, the example is limited to a sodium based battery, and has not been attempted for a lithium battery.
As another example of the conventional art, sodium iron fluorophosphate (Na 2 FePO 4 F) has been used as a cathode material for a lithium secondary battery, and the structure of Na 2 FePO 4 F and its electrochemical characteristics have been disclosed. However, iron-based Na 2 FePO 4 F suffers from a major disadvantage as a cathode material because it has a low charge/discharge potential (about 3.5 V), which is similar to an iron-based olivine material. Attempts to overcome this disadvantage of Na 2 FePO 4 F have been made by using manganese-based Na 2 MnPO 4 F, which has a higher potential (4V) compared to iron-based Na 2 FePO 4 F. Unfortunately, Na 2 MnPO 4 F also suffers from a major disadvantage as a cathode material because of electrochemical inactivity due to the low electrical conductivity of a polyanion-based material.
The above information disclosed in this Background section is only for enhancement of understanding of the background of the invention.
SUMMARY OF THE DISCLOSURE
The present invention provides compositions and methods of manufacturing a cathode for a lithium secondary battery, in which nano-sized particles reduce the diffusion length of lithium, and the deintercalation of sodium and the intercalation of lithium are carried out through a chemical method. Consequently, in the improved cathode of the invention, the diffusion path of lithium can be previously established, thereby improving the electrochemical properties of the cathode of the lithium secondary battery.
In one aspect, the present invention provides a composition for a secondary battery cathode that includes a compound represented by the formula Li x Na 2-x MnPO 4 F, which is prepared by chemical intercalation of lithium into Na 2 MnPO 4 F.
In another aspect, the present invention provides a method for preparing a cathode for a secondary battery, the method including: (i) synthesizing Na 2 MnPO 4 F with a controlled particle size; and (ii) carrying out lithium intercalation and sodium deintercalation by an ion exchange method.
According to one aspect of the present invention, it is possible to use manganese fluorophosphate including lithium as a cathode material with a high electrochemical potential by chemically intercalating lithium into Na 2 MnPO 4 F with a controlled particle size through an ion exchange method. Advantageously, this method establishes a lithium diffusible site or pathway within the cathode material, thereby making it possible to obtain a high charge/discharge property, compared to that of a cathode produced from the same size of a Na 2 MnPO 4 F cathode material not including lithium. According to the invention, when the above described cathode material is applied to the cathode of a secondary battery, it is possible to achieve a maximum capacity of at least 4 times higher than that of the same primary particle size of Na 2 MnPO 4 F.
Other aspects and exemplary embodiments of the invention are discussed infra.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other features of the present invention will now be described in detail with reference to certain exemplary embodiments thereof illustrated in the accompanying drawings which are given hereinbelow by way of illustration only, and thus are not limitative of the present invention, and wherein:
FIG. 1 shows a crystal structure of Li x Na 2-x MnPO 4 F, in which octahedral MnO 4 F 2 and tetrahedral PO 4 form a framework, and there exists a channel through which lithium and sodium can be intercalated and deintercalated;
FIG. 2 shows electron microscopic images of a cathode material prepared by Example 3 of the present invention, in which FIGS. 2 a and 2 b show the cathode material before and after ion exchange, respectively;
FIG. 3 shows charge/discharge curve graphs of a cathode material prepared according to the methods of Example 1 of the present invention, at room temperature;
FIG. 4 shows charge/discharge curve graphs of a cathode material prepared according to the methods of Example 1 of the present invention, at room temperature; and
FIG. 5 shows discharge curve graphs of cathode materials prepared according to the methods of Examples 1 to 3, in which a change in a discharge curve according to the amount of intercalated lithium is shown.
It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various preferred features illustrative of the basic principles of the invention. The specific design features of the present invention as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes will be determined in part by the particular intended application and use environment.
DETAILED DESCRIPTION
Hereinafter reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it will be understood that the present description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.
Unless specifically stated or obvious from context, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. “About” can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term “about.”
Ranges provided herein are understood to be shorthand for all of the values within the range. For example, a range of 1 to 50 is understood to include any number, combination of numbers, or sub-range from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, as well as all intervening decimal values between the aforementioned integers such as, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9.
The present invention provides a cathode material for a lithium secondary battery, which includes a manganese-based fluorophosphate compound represented by the following Formula:
Li x Na 2-x MnPO 4 F
The cathode material for a secondary battery, which includes the Formula above, has a primary particle size of about 300 nm or less, is coated with carbon for improvement of conductivity, and shows a potential plateau in discharging of about 3.7 V to about 4.0V.
The present invention also provides a method for producing a cathode material for a lithium secondary battery, the method including:
(i) uniformly mixing sodium (Na) oxide or a precursor thereof, manganese (Mn) oxide or a precursor thereof, phosphate (P) or a precursor thereof, and fluoride (F) or a precursor thereof through ball milling, and carrying out pretreatment on the obtained mixture, followed by firing to synthesize Na 2 MnPO 4 F; and
(ii) intercalating lithium into the cathode material synthesized in step (i) through an ion exchange method to synthesize Li x Na 2-x MnPO 4 F.
According to a preferred embodiment of the present invention, in step (i) the mixture is uniformly mixed for about 6 hours through ball milling, and then subjected to pretreatment under an air atmosphere at about 300° C. for about 2 hours.
According to a preferred embodiment of the present invention, step (ii) includes the step of intercalating lithium ions into the cathode material obtained from step (i) through lithium intercalation/sodium deintercalation by an ion exchange method.
According to a preferred embodiment of the present invention, step (ii) includes the step of chemically deintercalating sodium from the cathode material synthesized from the step (i), and chemically intercalating lithium into the cathode material.
According to a preferred embodiment of the present invention, the cathode material obtained from step (ii) is uniformly mixed with a carbon conductive material at a ratio of about 60:40 to about 90:10, followed by ball milling. It is contemplated within the scope of the invention that the aforementioned range includes all sub-ranges within the specified range. For example, the ratio of cathode material to carbon conductive material may range from about 60:40 to about 61:39, 62:38, 63:37, 64:36, 65:35, 66:34, 67:33, 68:32, 69:31, 70:30, 71:29, 72:28, 73:27, 74:26, 75:25, 76:24, 77:23, 78:22, 79:21, 80:20, 81:19, 82:18, 83:17, 84:16, 85:15, 86:14, 87:13, 88:12, 89:11, or 90:10. Similarly, the ratio of cathode material to carbon conductive material may range from about 90:10 to about 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:35, 64:36, 63:37, 62:38, 61:39, or 60:40. It is further contemplated within the scope of the invention that the ratio of cathode material to carbon conductive material may include all intervening ratios, for example, about 60:40, about 61:39, about 62:38, about 63:37, about 64:36, about 65:35, about 66:34, about 67:33, about 68:32, about 69:31, about 70:30, about 71:29, about 72:28, about 73:27, about 74:26, about 75:25, about 76:24, about 77:23, about 78:22, about 79:21, about 80:20, about 81:19, about 82:18, about 83:17, about 84:16, about 85:15, about 86:14, about 87:13, about 88:12, about 89:11, and about 90:10, as well as all intervening decimal values. Then, the carbon conductive material is uniformly coated on a cathode surface to improve the electric conductivity.
The precursor of the sodium oxide may be selected from sodium phosphate, sodium carbonate, sodium hydroxide, sodium acetate, sodium sulfate, sodium sulfite, sodium fluoride, sodium chloride, sodium bromide, and any mixture thereof.
According to the present invention, the precursor of the manganese oxide may be selected from manganese metal, manganese oxide, manganese oxalate, manganese acetate, manganese nitrate, and any mixture thereof. The precursor of phosphate may be selected from ammonium phosphate, sodium phosphate, potassium phosphate, and any mixture thereof.
Furthermore, LiBr or LiI may be used to cause ion exchange between lithium and sodium during the intercalation of lithium by the ion exchange method. The carbon conductive material may be citric acid, sucrose, Super-P, acetylene black, Ketchen Black, carbon or any combination of the foregoing.
Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.
The present invention provides a cathode material for a secondary battery, which includes a compound represented by the Formula:
Li x Na 2-x MnPO 4 F, where 0<x<2.
In an exemplary embodiment, the cathode material includes both lithium and sodium, shows a potential discharge plateau at about 3.7 V to about 4.0V, and is coated with carbon for conductivity improvement.
Hereinafter, the method for producing a cathode material for a secondary battery, according to the present invention will be described. The specific production method will be more easily understood through the following Examples.
For example, the cathode material Na 2 MnPO 4 F for a secondary battery is prepared by uniformly mixing sodium oxide or a precursor thereof, manganese oxide or a precursor thereof, phosphate or a precursor thereof, and fluoride or a precursor thereof through ball milling, carrying out pretreatment on the mixture, and carrying out heat treatment by firing the mixture obtained from the pretreatment. According to the invention, the prepared Na 2 MnPO 4 F has a particle size of about 1 μm or less, and an average particle size of about 300 nm. Na 2 MnPO 4 F prepared according to the invention is introduced into an acetonitrile solution including, for example, LiBr dissolved therein. Then, Argon gas is flowed into the solution while the temperature is raised so that ion exchange between lithium and sodium can be carried out. By washing and drying the resultant product of the ion exchange, a cathode material, manganese fluorophosphate Li x Na 2-x MnPO 4 F, is obtained.
In order to increase electrical conductivity, the obtained cathode material, Li x Na 2-x MnPO 4 F, was subjected to carbon coating.
The precursor of the sodium oxide may be any suitable sodium containing compound including, but not particularly limited to, sodium carbonate, sodium hydroxide, sodium acetate, sodium sulfate, sodium sulfite, sodium fluoride, sodium chloride, sodium bromide, and any mixture thereof.
The precursor of the manganese oxide may be any suitable manganese containing compound including, but not particularly limited to, manganese metal, manganese oxide, manganese oxalate, manganese acetate, manganese nitrate, and any mixture thereof.
The precursor of phosphate may be any suitable phosphate containing compound including, but not particularly limited to, lithium phosphate, sodium phosphate, potassium phosphate and any mixture thereof.
The precursor of fluorine may be any suitable fluorine containing compound including, but not particularly limited to, metal fluoride, fluoride, and a mixture thereof.
The lithium source used for the ion exchange may be any suitable lithium containing compound including, but not particularly limited to, LiBr, LiI, or any lithium compound mixture suitable for causing ion exchange.
The solvent used for the ion exchange may be any solvent suitable for including, but not limited to, acetonitrile. The carbon conductive material may be, but is not particularly limited to, citric acid, sucrose, super-P, acetylene black, Ketchen Black, or any suitable carbon material.
The cathode material of the exemplary embodiment of the present invention prepared as described above may be used for manufacturing a lithium secondary battery. Herein, the manufacturing method is the same as a conventional lithium secondary battery manufacturing method except for the application of the cathode material. Hereinafter, the configuration and the manufacturing method of the secondary battery will be briefly described.
First, in a manufacturing process for a cathode plate using the inventive cathode material, the cathode material is added with one, two, or more kinds of conventionally used additives, such as, for example, a conductive material, a binding agent, a filler, a dispersing agent, an ion conductive material, and a pressure enhancer, as required, and the mixture is formed into a slurry or paste with an appropriate solvent (such as, e.g., an organic solvent). Then, the obtained slurry or paste is applied to an electrode supporting substrate by an appropriate technique such as, for example, the “doctor blade” method, etc., and then dried. Then, through pressing by rolling a roll, a final cathode plate is manufactured.
According to the invention, examples of the conductive material include graphite, carbon black, acetylene black, Ketchen Black, carbon fiber, metal powder, and the like. The binding agent may include, but is not limited to, PVdF, polyethylene, and the like. The electrode supporting substrate (collector) may include, but is not limited to, a foil or a sheet made of copper, nickel, stainless steel, aluminum, carbon fiber, or the like.
By using the cathode plate prepared as described above, a lithium secondary battery is manufactured. The lithium secondary battery may be manufactured into a variety of different shapes including, but not limited to, a coin shape, a button shape, a sheet shape, a cylindrical shape, or a square shape. Also, an anode, an electrolyte, and a separator for the lithium secondary battery are the same as those used in a conventional lithium secondary battery.
According to the exemplary embodiment of the present invention, the anode material may be a graphite-based material that does not include lithium. Additionally, the anode material may also include one, two, or more kinds of transition metal composite oxides including lithium. The anode material may also include, silicon, tin, etc.
The electrolyte may be, but is not limited to, a non-aqueous electrolyte including lithium salt dissolved in an organic solvent, an inorganic solid electrolyte, or a composite of an inorganic solid electrolyte. The solvent for the non-aqueous electrolyte may be, but is not limited to, one, two, or more solvents selected from the group including esters (such as, e.g., ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate), lactones (such as, e.g., butyl lactone), ethers (such as, e.g., 1,2-dimethoxy ethane, ethoxy methoxy ethane), and nitriles (such as, e.g., acetonitrile). Examples of lithium salt of the non-aqueous electrolyte may include, but is not limited to, LiAsF 6 , LiBF 4 , LiPF 6 , or the like.
Also, as the separator, a porous film prepared from a polyolefin such as, for example, PP and/or PE, or a porous material such as non-woven fabric may be used.
EXAMPLES
Hereinafter, the following examples are provided to further illustrate the invention, but they should not be considered as the limit of the invention. The following examples illustrate the invention and are not intended to limit the same.
Example 1
Sodium carbonate (Na 2 CO 3 ), manganese oxalate.hydrate (MnC 2 O 4 .2H 2 O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO 3 ), and ammonium phosphate (NH 4 H 2 PO 4 ) were introduced in predetermined amounts with respect to the total amount of 10 g, and ball milled for 6 hours to uniformly mix the materials.
The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 500° C. for 6 hours under an argon gas atmosphere. Then, the resulting Na 2 MnPO 4 F was precipitated in acetonitrile including 0.6 M of LiBr dissolved therein, and reacted together with the flow of argon gas at a temperature of 80° C.
The test sample, in which ion exchange was completed, was washed with anhydrous ethanol to remove the remaining NaBr, and subsequently dried. Then, the resulting test sample was uniformly mixed with Super-P in a ratio of 75:25 by ball-milling and then, prepared as a cathode material composite.
Example 2
Sodium carbonate (Na 2 CO 3 ), manganese oxalate.hydrate (MnC 2 O 4 .2H 2 O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO 3 ), and ammonium phosphate (NH 4 H 2 PO 4 ) were introduced in predetermined amounts with respect to the total amount of 10 g, and ball milled for 6 hours to uniformly mix the materials.
The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 500° C. for 6 hours under an argon gas atmosphere. Then, the resultant Na 2 MnPO 4 F was precipitated in acetonitrile including 1.0 M of LiBr dissolved therein, and reacted together with the flow of argon gas at a of 80° C.
The test sample, in which ion exchange was completed, was washed with anhydrous ethanol to remove the remaining NaBr, and subsequently dried. Then, the resulting test sample was uniformly mixed with Super-P in a ratio of 75:25 by ball-milling, and then prepared as a cathode material composite.
Example 3
Sodium carbonate (Na 2 CO 3 ), manganese oxalate.hydrate (MnC 2 O 4 .2H 2 O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO 3 ), and ammonium phosphate (NH 4 H 2 PO 4 ) were introduced in predetermined amounts with respect to the total amount of 10 g, and ball milled for 6 hours to uniformly mix the materials.
The resultant mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 500° C. for 6 hours under an argon gas atmosphere. Then, the resulting Na 2 MnPO 4 F was precipitated in acetonitrile including 2.5 M of LiBr dissolved therein, and reacted together with the flow of argon gas at a temperature of 80° C.
The test sample, in which ion exchange was completed, was washed with anhydrous ethanol to remove remaining NaBr, and subsequently dried. Then, the resulting test sample was uniformly mixed with Super-P in a ratio of 75:25 by ball-milling, and then prepared as a cathode material composite.
Comparative Example 1
Na 2 MnPO 4 F obtained under the same condition as described in Example 1, without an ion exchange step, was uniformly mixed with Super-P in a ratio of 75:25 by ball-milling, and then prepared as a cathode material composite.
Comparative Examples 2 to 4
Sodium carbonate (Na 2 CO 3 ), manganese oxalate.hydrate (MnC 2 O 4 .2H 2 % sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO 3 ), and ammonium phosphate (NH 4 H 2 PO 4 ) were introduced in predetermined amounts with respect to the total amount of 10 g, and ball milled for 6 hours to uniformly mix the materials.
The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 500° C. for 10 hours under an argon gas atmosphere. Then, the resultant Na 2 MnPO 4 F was precipitated in acetonitrile including 0.6 M (Comparative Example 2), 1.0 M (Comparative Example 3), or 2.5 M (Comparative Example 4) of LiBr dissolved therein, and reacted together with the flow of argon gas at a temperature of 80° C. The test sample, in which ion exchange was completed, was washed with anhydrous ethanol to remove the remaining NaBr, and subsequently dried. Then, the resulting test sample was uniformly mixed with Super-P in a ratio of 75:25 by ball-milling, and then prepared as a cathode material composite.
Comparative Examples 5 to 7
Sodium carbonate (Na 2 CO 3 ), manganese oxalate.hydrate (MnC 2 O 4 .2H 2 O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO 3 ), and ammonium phosphate (NH 4 H 2 PO 4 ) were introduced in predetermined amounts with respect to the total amount of 10 g, and ball milled for 6 hours to uniformly mix the materials.
The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 550° C. for 3 hours under an argon gas atmosphere. Then, the resulting Na 2 MnPO 4 F was precipitated in acetonitrile including 0.6 M (Comparative Example 5), 1.0 M (Comparative Example 6), 2.5 M (Comparative Example 7) of LiBr dissolved therein, and reacted together with the flow of argon gas at a temperature of 80° C. The test sample, in which ion exchange was completed, was washed with anhydrous ethanol to remove remaining NaBr, and subsequently dried. Then, the resulting test sample was uniformly mixed with Super-P in a ratio of 75:25 by ball-milling, and then prepared as a cathode material composite.
Comparative Examples 8 to 10
Sodium carbonate (Na 2 CO 3 ), manganese oxalate.hydrate (MnC 2 O 4 .2H 2 O), sodium fluoride (NaF), sodium hydrogen carbonate (NaHCO 3 ), and ammonium phosphate (NH 4 H 2 PO 4 ) were introduced in predetermined amounts with respect to the total amount of 10 g, and ball milled for 6 hours to uniformly mix the materials.
The resulting mixture was subjected to pretreatment at 300° C. for 2 hours under an air atmosphere, and fired at 550° C. for 6 hours under an argon gas atmosphere. Then, the resultant Na 2 MnPO 4 F was precipitated in acetonitrile including 0.6 M (Comparative Example 8), 1.0 M (Comparative Example 9), 2.5 M (Comparative Example 10) of LiBr dissolved therein, and reacted together with the flow of argon gas, at a temperature of 80° C. The test sample, in which ion exchange was completed, was washed with anhydrous ethanol to remove remaining NaBr, and subsequently dried. Then, the resultant test sample was uniformly mixed with Super-P in a ratio of 75:25 by ball-milling, and then prepared as a cathode material composite.
Experimental Example 1
Test on Electrode Performance
The primary particle size of cathode materials prepared from Examples 1 to 3, and Comparative Examples 1 to 10 was measured, and metal composition within the cathode materials was analyzed, by ICP emission spectrochemical analysis. The results are noted in Table 1.
TABLE 1
Composition analysis
LiBr
result (molar ratio)
molarity
Primary particle size
Li
Na
Mn
PO 4
Exp. 1
0.6M
300 nm
0.3
1.7
1.0
1.0
Exp. 2
1.0M
300 nm
0.6
1.4
1.0
1.0
Exp. 3
2.5M
300 nm
1.9
0.1
1.0
1.0
Comp. Exp. 1
—
300 nm
0.0
2.0
1.0
1.0
Comp. Exp. 2
0.6M
400 nm
0.13
1.87
1.0
1.0
Comp. Exp. 3
1.0M
400 nm
0.3
1.70
1.0
1.0
Comp. Exp. 4
2.5M
400 nm
0.65
1.35
1.0
1.0
Comp. Exp. 5
0.6M
500 nm
0.1
1.9
1.0
1.0
Comp. Exp. 6
1.0M
500 nm
0.2
1.8
1.0
1.0
Comp. Exp. 7
2.5M
500 nm
0.4
1.6
1.0
1.0
Comp. Exp. 8
0.6M
700 nm
0.08
1.92
1.0
1.0
Comp. Exp. 9
1.0M
700 nm
0.17
1.83
1.0
1.0
Comp. Exp. 10
2.5M
700 nm
0.35
1.65
1.0
1.0
It was found that as the primary particle size decreased, the amount of lithium intercalated into Li x Na 2-x MnPO 4 F by ion exchange at the same concentration of LiBr increased. In particular, when the primary particle size ranged from 700 nm to 400 nm, the amount of intercalated lithium was slightly increased according to the decrease of the particle size. However, when the particle size was 300 nm, the amount of intercalated lithium was highly increased. This indicates that lithium intercalation through a chemical method highly depends on the primary particle size. Accordingly, it has been found that in order to intercalate lithium into Na 2 MnPO 4 F through a chemical method such as ion exchange, it is important to control the particle size. Applicants have discovered that the primary particle size required for effective lithium intercalation by a chemical method is about 300 nm or less. Accordingly, the ball milling conditions and the heat treatment conditions of the starting material are important. As described herein, the control of the particle size was carried out by controlling the ball milling conditions and the heat treatment conditions; however, one of ordinary skill in the art will understand that these conditions may vary according to the types of devices and procedures used for the aforementioned methods. The important aspect is that chemical lithium intercalation is efficient only when the primary particle size is controlled to a predetermined size or less. Accordingly, it is contemplated within the scope of the invention that any methods that produce a primary particle size of about 300 nm or less may be used. According to the invention, it is possible to prepare Li x Na 2-x MnPO 4 F including both lithium and sodium.
By using powder of the cathode material composites from Examples 1 to 3 and Comparative Examples 1 to 10, 95 wt % of cathode material composite was mixed with 5 wt % of binding agent PVdF, and then a slurry was prepared by using N-methylpyrrolidone (NMP) as a solvent.
The slurry was applied to aluminum (Al) foil with a thickness of 20 μm, and then dried and consolidated by press. The resulting product was dried under a vacuum at 120° C. for 16 hours, to provide a circular electrode with a diameter of 16 mm.
As a counter electrode, a lithium metal foil punched with a diameter of 16 mm was used, and a polypropylene (PP) film was used as a separator. Also, as an electrolyte, a solution containing 1 M LiPF 6 in ethylene carbonate (EC) and dimethoxy ethane (DME) mixed in a ratio of 1:1 (v/v) was used. The electrolyte was impregnated in the separator, and the separator was positioned between the operating electrode and the counter electrode. Then, the electrode performance of a battery was tested by using a case (SUS) as an electrode test cell. The measurement results including discharge capacity are noted in Table 2 below.
TABLE 2
Discharge capacity at room
Discharge
temperature (mAhg −1 )
voltage (V)
Exp. 1
140
1.0
Exp. 2
178
1.0
Exp. 3
197
1.0
Comp. Exp. 1
55
1.0
Comp. Exp. 2
83
1.0
Comp. Exp. 3
112
1.0
Comp. Exp. 4
134
1.0
Comp. Exp. 5
72
1.0
Comp. Exp. 6
98
1.0
Comp. Exp. 7
129
1.0
Comp. Exp. 8
43
1.0
Comp. Exp. 9
54
1.0
Comp. Exp. 10
97
1.0
As shown in FIG. 2 , when the surface of a test sample from Example 3 was observed by an electron microscope before and after ion exchange treatment, it was observed that the surface of the test sample after ion exchange became rough due to deintercalation of sodium and intercalation of lithium.
The change in the charge/discharge characteristics resulting from ion exchange, was determined by comparing data from Example 1 and Comparative Example 1 (see FIGS. 3 and 4 ). When ion exchange was not carried out, Na 2 MnPO 4 F showed a discharge capacity of 55 mAhg −1 . On the other hand, when 0.3 of lithium was intercalated into Na 2 MnPO 4 F by ion exchange to produce Li 0.3 Na 1.7 Mn 2 PO 4 F, the discharge capacity was 140 mAhg −1 , which was 2.5 times higher than that of Na 2 MnPO 4 F alone. Since only 0.3 lithium was intercalated, it was possible to achieve a higher discharge capacity than Na 2 MnPO 4 F including only sodium. Thus, it has been found that intercalation of lithium has a significant beneficial effect by increasing the electrochemical capacity of manganese-based fluorophosphate. Additionally, as shown in FIG. 5 , increasing the amount of intercalated lithium from 0.3 to 1.9 (Examples 1 to 3), further increased the discharge capacity from 140 mAhg −1 to 197 mAhg −1 . From these results, it has been determined that intercalation of lithium into manganese-based fluorophosphate has a significant beneficial effect by increasing electrochemical capacity. Without being bound by theory, it is believed that this is because the intercalated lithium establishes a pathway for lithium diffusion, which has a positive effect on lithium intercalation/deintercalation or sodium intercalation/deintercalation during charging/discharging.
The invention has been described in detail with reference to exemplary embodiments thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
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Disclosed are compositions and methods for producing a cathode for a secondary battery, where a fluorophosphate of the formula Li x Na 2-x MnPO 4 F is used as an electrode material. Li x Na 2-x MnPO 4 F is prepared by partially substituting a sodium site with lithium through a chemical method. Li x Na 2-x MnPO 4 F prepared according to the invention provides a cathode material for a lithium battery that has improved electrochemical activity.
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BACKGROUND OF THE INVENTION
The invention relates to a method for filtering a liquid, in which at least one filtering aid is added to the dirty liquid to be filtered and a higher degree of purity is achieved.
A method for cleaning liquid cooling lubricants is known from the German patent 35 37 384. For this method, a pre-coated filter is disposed in a cycling system and filtering aids with a highly surface-active and adsorbing substance are used in the pre-coated filter. These filtering aids are, for example, conventional commercial fuller's earths. It is a disadvantage of the system that, to begin with, a filter cake of the filtering aid must be built up, so that a sufficient degree of filtration results. It must therefore be expected that the input of filtering aid will be high. A further disadvantage can be seen therein that a precise dosing of the pre-coating layer is a problem because of turbulences and that the filtration result is therefore subject to high fluctuations under some circumstances.
SUMMARY OF THE INVENTION
It is an object of the invention, to provide a method and an apparatus for filtering a liquid, for which the amount of filtering aid used is to be minimized and a high filtration quality is to be achieved in filtration plants.
This objective is accomplished by the by the method and apparatus as described and claimed hereinafter.
The advantage of the method lies therein that an initial pre-coating is not required. Instead, filtering aid is added to the dirty liquid that is to be filtered. By these means, a high degree of purity can be achieved.
According to a refinement of the invention, it is proposed that the open-pore character be assured by appropriately dosing the filtering aid. For this measure, especially an appropriate particle size of the filtering aid or an appropriate compression strength of the filtering aid is especially important for avoiding any caking.
According to a refinement of the invention, the filtering aid can be dosed in continuously or discontinuously. The inoculation advantageously is discontinuous if the input of dirt is very low or if the service life of a filtration plant is to be prolonged. Filtering aids can also be added when the plant is not in operation and it is only necessary to maintain the quality of the liquid.
Pursuant to a further development of the invention, the filtering aid is pre-mixed with the dirt components or with the dirty liquid, so that a better distribution of the filtering aid takes place. Advantageously, either crushed corn or also cellulose can be used. Especially the inoculation with cellulose achieves a filtration quality, which is better than that achieved with the previously used pre-coating with diatomaceous earth or fuller's earth. Since it is injurious to health, special diatomaceous earth should be avoided in the future.
The fact that the residue can be disposed of easily is a further advantage of the use of crushed corn or cellulose. Cellulose, for example, burns almost without leaving any residue.
It has turned out that the invention can be employed advantageously in different filtration plants. The filtering aid increases the lifetime of the liquid, for example, of an emulsion. In addition, a degree of filtration of less than 15 μ is achieved. The filtration plants include, for example, gravity belt filtration plants, pressure belt filtration plants or vacuum filtration plants.
In a further variation of the method, a filtration plant is pre-coated only partially, that is, the filtering aid covers only a certain region of the effective filter surface.
As a result, a sort of partial flow filtration results. The essential advantage is seen therein that two filters can be integrated into a single filtration system. Likewise, it is possible to carry out the pre-coating at different densities. By these means also, filters with different degrees of filtration are formed.
An additional variant of the invention is represented by the basic pre-coating of the filtering aid. In this variant, initially only the filtering aid is introduced. Subsequently, the dirty liquid is added. This basic pre-coating has the advantage that a high degree of filtration is achieved at the very start of the filtration process. Quite generally, the invention exhibits the following improvements in comparison to previously known methods:
reduction in the consumption of filtering aid;
avoidance of the use of filtering aids, injurious to health, such as diatomaceous earth in pre-coated filtration plants;
increase in the quality of the filtration;
replacement of pre-coated filtration plants as state of the art technology for high-degree and very high-degree filtration requirements when cooling lubricants are used, both in the case of oil as well as in the case of suspensions;
the possibility of working up spent oils;
prolonging the maintenance interval for cooling lubricants;
reducing the costs of cleaning storage containers for cooling lubricants;
reducing the problem of disposing of waste materials;
reducing the costs of the disposal.
These and further distinguishing characteristics of preferred further developments of the invention are evident from the claims as well as from the specification and the drawings. The individual distinguishing features can be realized by themselves alone or in the form of sub-combinations of several for the embodiment of the invention and in other fields and represent advantageous, patentable developments, for which protection is claimed here.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be described hereinafter with reference to working examples. In the drawings
FIG. 1 shows the diagrammatic construction of a plant for purifying liquid cooling lubricants;
FIG. 2 shows a variation of a plant for purifying liquid cooling lubricants.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows the diagrammatic construction of a plant for purifying liquid cooling lubricants. The cooling lubricant, supplied by machine tools, which are not shown here, and contaminated with chips, turnings, slivers and other impurities, is passed into a dirty container 13 via pipelines 10 , 11 , 12 . From this dirty container 13 , the liquid passes through pipeline 14 and a pump 15 into a pre-coated filtration plant 16 . Usually, there are several cartridge filters in a precoated filtration plant. Such a pre-coated filtration plant is known, for example, from DE 29 08 625 A1.
The purified liquid leaves the plant through pipeline 17 and can be returned once again to the machine tools by way of a clean tank and possibly additional pumps. A pipeline 18 and a valve 19 are disposed at the discharge opening of the pre-coated filtration plant 16 . When the valve 19 is opened, the dirt and the filtering aid are pumped into a container 20 .
A filtering aid for the basic pre-coating, such as cellulose, passes from a container 21 into a delivering device 22 . This delivering device has dosing equipment 23 and a screw conveyor 24 . From here, the filtering aid is dosed into a container 25 , which is filled with oil or suspension. The filtering aid and the liquid are mixed with a stirrer 26 . This means that, at the start of the filtration, initially the basic pre-coating is prepared and pumped to the filter. At the end of the basic pre-coating, the pre-coated filtration plant is ready to function. During the normal filtration cycle, oil inoculation substance is added continuously or also discontinuously via pipeline 27 and valve 28 together and simultaneously with the filtration cycle from the inoculation container 25 to the filtration cycle, that is, oil inoculation substance is inoculated continuously or discontinuously with an inoculation pump 29 into the filtration cycle. In order to avoid unnecessary expenditure of energy, this is done preferably by injecting the inoculation substance via pipeline 27 into the pipeline 14 .
Due to the inoculation method, the dirty liquid, pumped through the filter cartridges, is mixed constantly with inoculating substance, so that a mixture, consisting of inoculating pre-coating agent and dirt, is formed on the filter cartridges. Owing to the fact that inoculating pre-coating substance is inoculated continuously or discontinuously during the filtration, the porosity of the deposits on the filter cartridges is increased and the property of the coating improved, so that the filtration is very effective and of a high quality. Likewise, the service life is clearly prolonged by the inoculation.
To form a basic pre-coating, the basic pre-coating agent, as is shown in the Figure, is provided in a container 30 and supplied from there to transporting equipment 31 , consisting of dosing equipment 32 and a screw conveyor 33 . The screw conveyor transports the basic pre-coating into the container 34 , which contains the oil or the suspension. With the stirrer 35 , the basic pre-coating is mixed with the oil or suspension and supplied via pipeline 36 and valve 37 to the pre-coated filtration plant before the start of the filtration process. At the same time, the basic pre-coating is deposited on the filter cartridge and forms a first filtration layer.
Due to the subsequent inoculation of the dirty liquid supplied, a better quality of cooling lubricant is achieved, that is, the degree of purity of the cooling lubricants is increased.
The variant of FIG. 2 shows a construction, in which certain parts of the plant, such as the filtering equipment or certain conveying pumps, are constructed in duplicate. The plant consists of a clean container 38 , which contains the purified cooling lubricant, a dirty container 39 , two filtration devices 40 , 41 , an inoculation device consisting of an inoculation container 42 , a dosing device 43 , a pre-coating container 44 as well as an appropriate complement of pumps and pipelines. The cooling lubricant, which is to be cleaned, passes from machine tools, which are not shown here, via pipelines 45 , 46 to a dirty container 39 . The dirty liquid is pumped via several pumps 48 and the pipelines 49 , 50 to the two filtration devices 40 , 41 . Filtering aid is supplied to the suction side of these pumps 48 through pipelines 51 , 52 . The filtering aid, such as crushed corn, is made available in a container 53 and, from there, reaches the inoculation container 42 via conveying equipment 54 and a screw conveyor 55 . The inoculation container contains clean liquid. The filtering aid is mixed with the clean liquid in this container. For this purpose, a mixer 56 is provided.
As already mentioned, the clean liquid with the filtering aid passes through conveying pumps 57 , 58 and pipelines 51 , 52 into the suction side of the pumps 48 . The dirty liquid, now mixed with the filtering aid, is supplied to the filtration devices 40 , 41 . In the filtration devices, filter cartridges, for example, are disposed, which have a certain filter fineness and on which the dirt is deposited. The purified liquid passes through pipelines 59 , 60 into the clean container 38 and can be conveyed from there by pumps 61 and pipeline 70 to the appropriate machine tools. For cleaning the filtration devices 40 , 41 , compressed air is supplied via pipelines 62 , 63 . This compressed air displaces the clean liquid and, at the same time, extracts moisture from the filter cake, which is formed by the filtration. The filter cake is passed through pipelines 64 , 65 to a washing container 44 . The dirt is discharged from the washing container with pumps 66 into a pressure belt filter 67 . This pressure belt filter separates the remaining moisture from the sludge. The sludge is discharged into the container 68 , and the remaining liquid passes through pipeline 69 into the dirty container 39 .
Of course, different systems can be used for the filtration. For example, the possibility exists of using gravity filtration or vacuum filtration. In the case of vacuum filtration, the filtering aid is deposited on an endless belt. This endless belt passes through the filter container. The dirt, deposited on the belt, is removed by appropriate scraping equipment.
Filtering aid can also be charged even when no dirt is being charged. This is for the purpose of maintenance filtration, which is required particularly on weekends, and thereby makes possible a longer useful life of the cooling lubricant.
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A method for filtering a liquid and an apparatus for carrying out the method in which at least one container is provided from which a filtering aid is fed to a dosing device by a delivery device, and the filter aid is supplied to an injecting container and/or to a filter element via the dosing device.
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FIELD OF THE INVENTION
This invention relates to the utilization of tracers in connection with monitoring hydrocarbon reservoirs and/or monitoring wellbores penetrating hydrocarbon reservoirs.
BACKGROUND OF THE INVENTION
The term tracer has generally been used to denote a material which is deliberately introduced into fluid flow which is taking place. Detection of the tracer(s) downstream of the injection point(s) provides information about the reservoir or about the wellbore penetrating the reservoir. In particular, deliberate addition of tracers has been used to observe flow paths and transit times between injection wells (used for instance to inject a water flood into a reservoir) and production wells. For this application of tracers to study inter-well flow, the tracer materials have generally been dissolved in the injection water at the surface before it is pumped down the injection well.
Some prior documents have proposed placing tracers in a well, or adjacent to it in a perforation extending through well casing into the surrounding formation, so as to monitor flow or events within the well rather than flow between wells. U.S. Pat. No. 507,771 proposed injecting radioactive tracers into perforations and monitoring loss of tracer with a wireline tool. U.S. Pat. No. 5,892,147 and U.S. Pat. No. 6,645,769 both proposed releasing distinguishable tracers from various underground locations within a wellbore and monitoring the produced flow to detect the presence of tracer. U.S. Pat. No. 6,840,316 proposed that tracer should be released under electrical control at various points within a complex hydrocarbon well and suggests a number of possible positions for sensors (of unspecified construction) to detect the presence of tracer.
In these various applications a deliberately added tracer may be present at very low concentration in the produced fluid where it is detected, and a number of prior documents have been concerned with choice of tracer material and methods of detection such that the tracer is detectable at very low concentrations. Substances deliberately introduced as tracers have included radioisotopes, fluorine-containing compounds and compounds of rare earth elements.
Whilst there are a variety of tracers and a variety of detection methods, a number of methods for detection of tracers involve the use of laboratory instruments. For example Society of Petroleum Engineers paper SPE 124689 proposes laser spectroscopy as a method of detection. WO2007/102023 proposes the use of a tracer containing a rare metal (e.g. caesium, hafnium, silver and gold) which is then detected in a sample by means of inductively coupled plasma mass spectrometry (ICP-MS).
When tracers are used, especially when the tracers do not contain radioactive isotopes, it is normal that samples are taken from the produced flow and sent away to a laboratory where solvent extraction or some other preparative procedure is carried out manually to extract and/or concentrate the tracer, after which the amount of tracer is determined by an analytical method which may be a sensitive instrumental technique. In consequence there is apt to be a significant time delay between taking the sample and obtaining an analysis of tracer(s) within it.
SUMMARY OF THE INVENTION
This invention provides a method of monitoring flow within a hydrocarbon well or a hydrocarbon reservoir penetrated by a well, comprising:
providing one or more tracer materials at one or more subterranean locations from which tracer may enter flow produced from the well, and monitoring flow within or from the well to detect the presence of one or more tracers in the flow,
characterized in that the detection of tracer is carried out by an electrochemical reaction.
The subterranean location(s) at which tracer is provided may be within the reservoir, or sufficiently close to the reservoir that tracer may flow into the well. In some forms of this invention the location(s) at which tracer is placed may be within part(s) of the well.
The step of monitoring flow may entail providing electrodes connected to a source of electrical potential, bringing a sample or portion of the flow into contact with the electrodes and applying potential to the electrodes to bring about electrochemical reaction, while measuring the current flow. This may be done using one of the various forms of voltammetry in which potential applied to the electrodes is varied over a range, while measuring the current flow as potential is varied.
The analytical detection of tracer by means of electrochemical reaction may serve to give qualitative detection of the presence of a tracer or may serve to give a quantitative determination of the concentration of tracer in the flow. A considerable advantage of using an electrochemical reaction as the analytical method is that it can be carried out with apparatus that can be small in size, that is easy to use and transport and that does not need the support of an extensively equipped laboratory. The electrochemical reaction mixture may be exposed to ambient air. Thus, it is practical for the analytical determination of tracers to be carried out proximate to the well so that the results can be available quickly after a sample is taken. Analysis of samples could for instance be carried out in an office at the site of the well, or nearby. Conveniently this may for instance be done within 10 km of the well, possibly closer such as within 3 km.
It will be necessary to choose a tracer or tracers which can be detected by means of an electrochemical reaction and also arrange that the tracer(s) will be released at a sufficient concentration to be detectable in the electrochemical reaction. We have found that electrochemical redox reactions can detect some tracers at concentrations which are sufficiently low to provide a useful level of sensitivity, which is of course of particular value when it is achievable with apparatus that does not require elaborate laboratory facilities.
The tracer may be a redox active material, capable of undergoing a reduction or oxidation reaction within an electrochemical cell. There are a number of possibilities for redox-active tracers.
The tracer may be an ionic species capable of undergoing a redox reaction. One possibility is a metal ion having more than one oxidation state. For instance copper ions provided by addition of copper sulphate solution can undergo electrochemical reduction to copper metal.
Some inorganic anions can be used. Halides such as chloride, bromide and iodide can undergo electrochemical oxidation to chlorate, bromate or iodate respectively. Thiocyanate ions can undergo electrochemical oxidation to trithiocyanate (SCN) 3 − while nitrate ions can undergo electrochemical reduction to nitrite. Nitrate and thiocyanate ions have the advantage that they are not normally encountered in subterranean water.
A number of organic molecules undergo electrochemical redox reactions and so are detectable electrochemically. Some instances are xanthine, ascorbic acid and barbituric acid.
In a significant development of this invention, the tracer is in the form of nanoparticles containing a metal which has more than one oxidation state. Such nanoparticles can be detected in very low concentration as will be explained further below.
The electrochemical reaction to determine the presence of one or more tracers in the flow may be carried out by the well established technique of cyclic voltammetry in which the potential applied to a working electrode is cycled over a sufficient range to bring about the oxidation and reduction reactions while recording the current flow as the potential is varied. The recorded current shows peaks at the potentials associated with the reduction and oxidation reactions. It is also possible that this variation in potential whilst recording current flow could be carried out over only a portion of the reduction and oxidation cycle. This would be classed as linear scan voltammetry.
Cyclic and linear scan voltammetry are customarily performed with a continuous variation of the applied potential over a range, keeping the rate of change sufficiently slow that the analyte is able to diffuse within the electrolyte to reach the working electrode. Further possibilities are that the applied potential is varied in steps (as in square wave voltammetry) or is varied as pulses (as in differential voltammetry for instance). A discussion of various voltammetry techniques can be found in for example Brett and Brett Electrochemistry Principles: Methods and Applications , Oxford University Press 1993. Square wave voltammetry has been found to be effective. In this technique the potential applied to the electrodes is varied in steps superimposed on a progressive variation over a range. The resulting waveform may be such that it can be referred to as a square wave superimposed on a staircase.
Sensitivity of these voltammetric methods may be increased by movement of the electrolyte relative to the working electrode, so that the mass transport to the electrode is enhanced.
A further electrochemical technique which gives very good sensitivity to the presence of some tracer(s) is stripping voltammetry with accumulation. This technique proceeds in two stages. In the first stage the working electrode is maintained at a potential which attracts tracer to become adsorbed onto it, possibly with a redox electrochemical reaction of the tracer on the electrode. The amount of tracer which accumulates is dependent on the concentration of tracer in the solution. Then in a second stage a voltammetric scan is carried out, bringing about electrochemical reaction of the material which has been accumulated on the electrode. This voltammetric scan also strips the accumulation from the electrode. This technique can be used with metal ions (e.g. cadmium, lead, bismuth or zinc) as tracers, the metal ions being reduced during the accumulation stage and re-oxidized during the subsequent voltammetric scan. Moreover, we have found that this technique of stripping voltammetry with accumulation can be used when the tracers are nanoparticles as mentioned above. The combination of nanoparticles as tracers and stripping voltammetry with accumulation as the method of detection leads to very good sensitivity to the tracer(s). The accumulation stage will generally be longer than the subsequent detection stage. Typically it will be more than 10 times longer.
A further possibility for enhancing sensitivity of voltammetry is to employ an electrode which spontaneously adsorbs the tracer, possibly by means of a substance which is chemically bound to the electrode surface and has binding affinity for the tracer. Detection would again have two stages: a first stage during which the tracer would be adsorbed and so accumulate on the electrode, followed by a second stage in which a voltammetric scan is carried out to detect, and preferably quantitatively determine, the amount of tracer.
These methods in which tracer(s) are accumulated on the electrode before detection may also be made even more sensitive by movement of the electrolyte relative to the working electrode during the accumulation stage, so that the mass transport to the electrode is enhanced.
Yet another possibility is to selectively extract tracer at the surface by bringing the flow into contact with a material capable of absorbing tracer, notably an ion exchange matrix. Any tracer retained by this matrix could subsequently be extracted into a solution which was then subjected to the electrochemical reaction to detect the presence of one or more tracers.
Apparatus for carrying out electrochemical determinations of tracer may comprise a container for the sample under test, a plurality of electrodes to be immersed in the sample and thus form an electrochemical cell, and a potentiostat to apply potential to the electrodes and measure current flow. The potentiostat may be operated under control of a computer which also records the results obtained.
The electrodes may constitute a conventional three electrode arrangement with a working electrode at which the electrochemical reaction occurs, a reference electrode and a counter electrode. These could be of standard types already used in electrochemistry.
An alternative to the use of separate electrodes of types traditionally used in electrochemistry is to use electrodes which screen printed (or deposited in some other way) onto an insulating substrate. Such electrodes may be manufactured as disposable items for one time only use, typically having a Ag/AgCl reference electrode, a metallic counter electrode and a carbon-based working electrode all screen printed on to a single ceramic or polymeric substrate.
A further possibility is that the working electrode is formed from boron-doped diamond located on an (electrically insulating) area of intrinsic diamond as described in U.S. Pat. No. 7,407,566. As shown in that document, such a working electrode may be carried on an insulating support of material other than diamond which also has a counter electrode and a reference electrode deposited on it.
It is possible that an arrangement with more than three electrodes could be used. There could be a single reference electrode and a single counter-electrode, but a number of working electrodes with specificity to different tracers.
The invention may be used in connection with various tasks which can be performed by use of tracers.
In one form of this invention tracers are used in conventional studies of inter-well flow from one or more injection wells to one more production wells. A tracer is added to the fluid which is pumped down an injection well, and thus is provided at the subterranean location where fluid exits from the injection well into the surrounding formation. This point of exit may be in a hydrocarbon reservoir or adjacent to it so that the injected fluid can be expected to flow through the formation to a production well. Whether the fluid actually does flow to the production well and how long it takes to travel from injection well to production well are of course questions which the addition of tracer is intended to investigate.
In these circumstances samples may be taken from fluid produced from a production well and examined by subjecting them to the electrochemical reaction. As mentioned earlier, this examination of the samples may be carried out close to the well site rather than by shipping the samples away to a laboratory elsewhere.
In another form, the invention may be used to observe flow within a well. This may possibly be in the context of a simple vertical well, releasing tracer at an underground location in the well (or close to it such as in a perforation which extends into the formation) and detecting its arrival at the surface. However, using this form of the invention to observe flow within a well is of particular interest within a more complex well which has multiple entry points for fluid from the formation around the well.
A well with multiple entry points for hydrocarbon may be any of:
a well which penetrates multiple pay zones (i.e. multiple oil-bearing formations);
a well which extends laterally within a reservoir, so that hydrocarbon enters the well at multiple points along the lateral;
a well which branches below ground so as to have multiple flow paths which merge before reaching the surface. A well which branches below ground may have branches diverging at angles to the vertical or may have multiple laterals.
For any well architecture where hydrocarbon can enter the well at multiple points, it will be desirable to have knowledge of what is flowing into the well at the various entry points, especially if the well has been provided with valves for control over the flow from different parts of the well.
Tracer materials may be provided at locations distributed within such a well or at locations within the formation and close to the wellbore, such as in perforations. Whenever tracer is placed in the formation adjacent to wellbore, the location at which the tracer is placed and from which it is released into the flow is preferably not more than 1 meter upstream from the point of entry into the wellbore.
One possibility here is that tracer is released from supply containers, in response to commands from the surface, analogous to the proposal in U.S. Pat. No. 6,840,316. An alternative is that the tracer is encapsulated within a body of other material which is exposed to the flow and is liberated into the flow as a consequence of diffusion out of the encapsulating material and/or degradation of the body of encapsulating material, analogous to techniques for the controlled release of other oilfield chemicals from encapsulation, described for instance in U.S. Pat. No. 5,922,652, U.S. Pat. No. 4,986,354, U.S. Pat. No. 6,818,594 and U.S. Pat. No. 6,723,683. Such bodies may be formulated to release tracer when in contact with water (more accurately subterranean brine) penetrating into the well so that detection of tracer in the downstream flow provides an indication that water penetration is taking place. Bodies of material which encapsulates tracer may be secured to equipment which is put into the well at the time of well completion. Another possibility is that material encapsulating tracer is applied as a coating on such equipment, for example on the exterior of a tubular.
Desirably, when this invention is used for monitoring flow from a plurality of separate entry points where water penetration into a well may occur, different tracers are associated with respective different entry points. By using different tracers at different locations within the well bore, the detection of tracer can indicate the part of the well where water penetration is taking place. This is useful in the context of a complex well with control valves which can be used to regulate (for instance to shut off) flow from a part of the well penetrated by water after that part of the well subject to water penetration has been identified by means of the tracer released into the water entering the well.
In a yet further form, this invention is used in monitoring a hydraulic fracturing job. This well-known method of stimulating a well involves pumping thickened fluid into the well and out into the formation, creating a fracture of the formation. U.S. Pat. No. 7,032,662 proposed incorporating tracers into the fracturing fluid which is injected and subsequently testing the flow back produced from the well to determine the amount of each tracer in the flow back. That determination of tracers in the flow back would then be used to estimate the amount of injected material which has returned to the surface. In an example, this document proposed that the tracers in produced fluid are determined by GC-mass spectrometry. The present invention could be used in analogous manner to monitor a fracturing job, but using an electrochemical method in accordance with this invention to detect and quantify tracers in produced fluid. This could be done in the vicinity of the well, rather than sending samples way to a laboratory.
As indicated above, it is envisaged that analysis for tracer by means of an electrochemical reaction will be carried out at the surface, in the vicinity of the well. However, it is also within the scope of this invention that the electrochemical analysis for tracer could be carried out underground, using a device analogous to that shown in US 2009090176 in which electrodes are exposed to a flow of fluid to be tested for tracer.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view showing two production wells surrounded by injection wells;
FIG. 2 diagrammatically illustrates equipment at the surface;
FIG. 3 shows equipment for the electrochemical determination of tracer;
FIG. 4 show part of a subterranean lateral, in cross-section;
FIG. 5 shows a well with a plurality of branches, in cross-section;
FIG. 6 shows a well being subjected to hydraulic fracturing;
FIG. 7 is a cyclic voltammogram obtained with copper sulphate in saline solution;
FIG. 8 is a series of square wave voltammograms obtained with barbituric acid in formation brine;
FIG. 9 is a plot of the peak heights in FIG. 8 against barbituric acid concentration;
FIG. 10 shows voltammograms obtained by applying stripping voltammetry to cadmium sulfide nanoparticles;
FIG. 11 is a plot of peak height against applied potential in the deposition stage of this stripping voltammetry;
FIG. 12 is a plot of peak height against electrode rotation rate in the deposition stage;
FIG. 13 is a plot of peak height against the duration of the deposition stage;
FIG. 14 shows a voltammogram obtained by applying stripping voltammetry to a mixture of three kinds of sulfide nanoparticles; and
FIG. 15 is a plot of peak height against concentration of lead sulfide nanoparticles.
DETAILED DESCRIPTION
FIG. 1 shows a typical arrangement where inter-well studies are required. Two production wells 10 are surrounded by six injection wells 12 used to inject water into the reservoir to drive oil towards the production wells. A question which has traditionally been addressed by use of tracers is whether the water from all of the injection wells is reaching the production wells. To investigate this, water-soluble tracers are added to the water flow into each injection well and the flow from each production well is then monitored for the presence of tracer.
As shown in FIG. 2 the flow produced from each production well 10 passes through a separator 14 which separates the flow into three parts, namely gas G. liquid crude oil 0 and water W (which will be saline because it includes some brine from the formation). Samples 16 are periodically taken from the water flow W by operation of valve 18 and tested for the presence of tracer.
In accordance with the present invention, this testing is carried out using electrochemistry and can be done in the vicinity of the well. An example of possible apparatus is shown in FIG. 3 . The sample 16 is placed in a beaker 20 and a set 22 of three electrodes in the form of strips deposited onto an insulating substrate, is placed dipping into the sample 16 in the beaker 20 . A potentiostat 24 is connected to the electrodes and is operated under control of computer 26 to carry out voltammetry serving to detect and quantify the tracers present.
FIGS. 4 and 5 illustrate a different application of tracers. The well illustrated by FIG. 4 has a long lateral which is subdivided into sections by packers 32 around the production tube 34 . One section between two packers 32 is shown in FIG. 4 . Within each section there is a valve arrangement which controls entry to the production tube 36 . Such a valve arrangement can be of conventional construction. As an example the arrangement shown in FIG. 4 comprises a sliding sleeve 36 which can be moved to cover and close openings 38 for entry of fluid into the production tube 34 , in response to a command transmitted from the surface.
A block of material 40 is secured to the exterior of the production tube 34 . This material 40 encloses a tracer (a different tracer in each section) and is such that the tracer is not released if the material 40 is exposed to oil but is released if the material 40 comes into contact with formation water or brine. The material 40 may be water-soluble so as to release tracer as the material 40 dissolves, or maybe water permeable, allowing tracer to dissolve into water which permeates into and out of the block of material 40 .
Consequently, so long as oil is entering each section of the wells lateral, no tracer is released. However if water penetrates into one section, tracer will be released into the water. This tracer can be detected at the surface in the same way as described above with reference to FIGS. 2 and 3 .
Detection of tracer at the surface will show that water penetration is occurring (which may of course also be apparent from an increase in the quantity of water produced) but because each section of the lateral is associated with a different tracer, identification of the tracer will also show which section of the lateral has suffered water penetration. The valve arrangement, 36 , 38 in that section can then be shut to prevent or restrict water entry, while allowing oil production from the other sections of the lateral to continue.
FIG. 5 diagrammatically illustrates a complex well drilled so as to have a plurality of branches 42 which merge below ground. When the completion of the well was carried out, valves 44 were incorporated which can be operated to restrict flow from a branch if needed. Each branch 42 may be subdivided into sections by packers 32 , with valves 46 (akin to sleeve 36 in FIG. 4 ) which can be used to shut off flow into a section of a branch. In particular, one of the valves 44 , 46 can be operated to shut off flow if water penetration into the flow becomes significant.
Similarly to the arrangement in FIG. 4 , blocks 40 of material enclosing tracers are secured to the exterior of the production tube 34 . These blocks 40 contain tracers (a different tracer in each section of each branch) which are released if the material 40 comes into contact with formation water or brine. Detection and identification of tracer at the surface will show where water penetration is occurring and the affected branch or part of a branch can be shut off by operation of the relevant valve 44 or 46 .
FIG. 6 illustrates the invention being used in connection with a hydraulic fracturing job. The different stages of fracturing and a range of thickeners which may be employed are well known and are not detailed here. Briefly, thickeners 50 are mixed with a supply 52 of water (as schematically indicated at 54 ) to form a fracturing fluid which is pumped into the production tube 56 of a well. Water-soluble tracer(s) 58 are also mixed into this fracturing fluid. The fracturing fluid flows out of the well as indicated at 60 and causes formation of a fracture 62 , with some fluid penetrating into the surrounding formation and depositing a filter cake 64 at the boundary of the fracture. After fracturing of the formation has taken place, fluid is allowed to flow back out of the well and is passed through an oil-water separator 14 so that there are separate flows of oil 66 and water 68 . Samples are taken from the water flow 62 and tested for the presence and amount of the tracer(s), by means of an electrochemical procedure in accordance with this invention. Detection and quantitative estimation of tracers in the samples allows the progress of flow back to be monitored and because this can be done in the vicinity of the well, the results are available with little or no delay, as flow back is progressing.
EXAMPLES
Example 1
One possible tracer which may be used in procedures as above is copper ions, conveniently provided as copper (II) sulfate. In order to demonstrate that this is detectable, a solution of 7 ppm copper (II) sulphate pentahydrate in a solution of 150 mM KCl in deionised water was subjected to cyclic voltammetry. A standard experimental setup was used, with a glassy carbon working electrode, a standard calomel electrode (SCE) as reference electrode and a platinum wire as counter electrode.
FIG. 7 shows the voltammogram obtained. It is a plot of current (in microamps) against applied potential (in volts) relative to the reference electrode. A sharp oxidative wave observed at approximately 0 volt (relative to SCE) is consistent with the oxidation of deposited Cu to Cu(I) whilst the oxidative wave at +0.15 volt is oxidation of Cu(I) to Cu(II). The scan was continued to +0.60 volt and then reversed. Two reductive waves were observed at +0.03 volt and −0.31 volt. These voltammetric signals represent the reduction of Cu(II) to Cu(I) and Cu(I) to elemental Cu respectively.
This demonstrates that copper ions provide a distinctive and easily identifiable voltammogram at concentrations below 10 parts copper sulphate pentahydrate per million.
Example 2
Another possible tracer is barbituric acid. A series of aliquots of this acid were added to a quantity of a formation brine (a saline solution reproducing the analysis of a North Sea formation brine). A square wave anodic voltammogram was taken after each addition had been mixed in. Voltammetry was carried out using a boron doped diamond working electrode, a standard calomel electrode (SCE) as reference and a platinum wire as counter electrode. The composition of the formation brine was: NaCl (27910 ppm), KCl (125 ppm), MgCl 2 (650 ppm), CaCl 2 (1700 ppm), SrCl 2 (250 ppm), BaCl 2 (20 ppm), and KHCO 3 (145 ppm) prepared in deionised water. The measured pH value of the formation brine was pH 7.6 (at ambient temperature). The square wave used in voltammetry had a frequency of 50 Hz; a step amplitude of 0.02 volt; and increased in potential by 0.002 volt at each step giving an overall scan rate of 0.1 volt/sec.
FIG. 8 shows the voltammograms obtained. In each of the voltammograms, a clearly resolvable, pronounced oxidative peak is apparent with peak potential centred at a redox potential of approximately 1 volt (relative to SCE). FIG. 9 shows the heights of this peak in microamp (after subtracting the baseline value) plotted against barbituric acid concentration and indicates that barbituric acid is detectable at concentrations of approximately 200 ppb and above.
Example 3
Synthesis of Nanoparticles
Synthesis of CdS nanoparticles was performed using Schlenk techniques under nitrogen.
The preparation method was based on arrested precipitation of cadmium sulfide from cadmium chloride solution as disclosed by Barglik-Chory, et al Synthesis, structure and spectroscopic characterization of water-soluble CdS nanoparticles (2003) Chemical Physics Letters, 379 (5-6), pp. 443-451 and is schematically illustrated by FIG. 4 . The starting materials were cadmium chloride CdCl 2 and hexamethyldisilathiane (HMSDT) which has the formula (CH 3 ) 3 Si—S—Si(CH 3 ) 3 . These were used together with glutathione which served as a water-soluble capping agent so as to produce nanoparticles of cadmium sulfide with glutathione residues bound to the nanoparticles' surface. Glutathione has the structure:
To prepare the nanoparticles, 3.228 g glutathione and 0.799 g CdCl 2 were first dissolved in 176 mL deionised water and stirred for 5 mins. Subsequently, 8.5 mL tetramethylammoniumhydroxide (TMAH) and 315 mL ethanol were added and after 10 mins this precursor solution was thoroughly degassed. 0.738 mL hexamethyldisilathiane (HMSDT) was added to the degassed solution, resulting in a clear (slightly yellow) colloidal solution of glutathione-capped CdS nanoparticles. The mixture was magnetically stirred for 1 hour and the prepared particles were precipitated by adding tetrahydrofuran (THF). One day later the supernatant was decanted and the precipitate was purified by re-dispersing it as a colloidal solution in a mixture of equal parts of water and THF and then precipitating again with THF. Finally, the supernatant liquid was decanted and the precipitate was dried under vacuum (<1 mbar).
ZnS and PbS nanoparticles were also prepared by the same procedure, using either zinc acetate or lead acetate in place of cadmium chloride.
Examination of these nanoparticles by scanning electron microscopy showed them to have particle diameter in a range 100-200 nanometres.
Example 4
CdS nanoparticles were dissolved at a concentration of 300 ppb in 0.1M phosphate buffer (pH7) which also contained 0.1M KCl. (Such nanoparticles can have a degree of water solubility in the presence of some anions, but here it is immaterial whether the solution of nanoparticles was a colloidal solution.) CdS nanoparticles were also dissolved at 300 ppb in formation brine of the composition given in Example 2. Each of these colloidal solutions was then subjected to stripping voltammetry using a rotatable glassy carbon working electrode (polished with 1 μm diamond paste before use) together with a standard calomel reference electrode and a platinum wire as counter electrode. The measurements were carried out using an Autolab III computer controlled potentiostat (Eco-Chemie, Netherlands).
To carry out the stripping voltammetry the glassy carbon (GC) electrode was held at a potential of −1.25 volt for a period of 30 seconds to electrochemically reduce and ‘deposit’ the CdS nanoparticles onto the GC electrode surface. This was the ‘deposition’ or ‘accumulation’ stage. During the deposition step the GC electrode was rotated at 1000 rpm to overcome mass-transfer limitations of the otherwise static solution, thus increasing the flow of CdS nanoparticles to the electrode surface.
The electrochemical deposition process, required for deposition of CdS nanoparticles prior to stripping, is believed to occur by a direct mechanism (see Merkoci et al. Nanotechnology, vol 18 (2007) article no. 035502) thus:
CdS+2H + +2 e − →Cd 0 +H 2 S
Following the accumulation stage, the ‘stripping/detection stage’ is invoked by scanning from −1.25 volt to +0.2 volt with a rising square wave having the same waveform as in Example 2.
The resulting voltammograms are shown in FIG. 10 . Both the sample prepared in phosphate buffer (indicated 70 ) and the sample prepared in formation brine (indicated 72 ) displayed well-defined, sharp oxidative stripping peaks. The peak current maxima were at approximately −0.85 volt (relative to SCE). Notably, the peak current magnitude and the potential at which peak current is observed are approximately the same for both samples, i.e. not sensitive to the composition of the cell solution.
Redox signals with the same peak positions and magnitudes were reproducibly obtained over several scans and furthermore the peak position and magnitude did not change if electrodes were polished between scans.
In typical produced water samples there is the unavoidable presence of a low concentration of organic species. In view of this, the above voltammetry was also carried out with approximately 5% by volume of hexane, pentane or dodecane added to the formation brine to represent hydrocarbon contaminants. It was observed that the distinctive peak was still present in the voltammetric signal and that the peak position and magnitude were not affected. This indicates that these nanoparticles would be detectable in produced water samples without extensive sample preparation.
Example 5
Optimisation of Stripping Voltammetry
CdS nanoparticles were dissolved at a concentration of 180 ppb in formation brine of the composition given in Example 2. This solution was then subjected to stripping voltammetry generally as in the preceding example, but with a deposition/accumulation time of 60 seconds and various potentials applied to the working electrode during the accumulation stage. FIG. 11 shows the height of the stripping current peak in microamp plotted against potential applied during accumulation. As shown in FIG. 11 , it was observed that progressively changing the applied potential from −1 volt to −1.75 volt, which was the optimum potential, led to a considerable increase in peak height. The reduction at −2 volt was attributed to interference from electrolysis of water leading to bubble formation on the electrode.
The above experiment was repeated, using an applied potential of −1.75 volt in the accumulation stage, progressively increasing the rotation rate of the glassy carbon electrode. FIG. 12 shows the height of the stripping current peak in microamp plotted against this rotation rate. As shown in FIG. 12 it was observed that a faster rotation rate during the accumulation stage increased the stripping peak current in the detection stage.
The experiment was then repeated again, using an applied potential of −1.75 volt and an electrode rotation rate of 3000 rpm, with variation in the length of time given to the accumulation stage. FIG. 13 shows the height of the stripping current peak in microamp plotted against the duration of the accumulation stage. As shown in FIG. 13 it was observed that a ten-fold increase in the duration of the accumulation stage led to a four-fold increase in the peak current in the detection stage. Thus the best conditions tested were a potential of −1.75 volt applied during a accumulation stage lasting 6000 seconds (ten minutes) with the electrode rotated at 3000 rpm. It is possible that even greater sensitivity would be achievable with still longer times and an even faster rotation rate, but the sensitivity was very good under the conditions tested.
Example 6
Detection of Other Nanoparticles
An attempt was made to detect nanoparticles of cadmium, zinc and lead sulfides on a GC working electrode, but only the cadmium sulfide particles were detected. This was rectified by using bismuth chloride as a coabsorbent, as taught by Wang et al J. Am. Chem. Soc., vol 125, pages 3214-3215 (2003)
Nanoparticles of CdS, ZnS and PbS were all dissolved at concentrations of 1000 ppb in formation brine of the composition given in Example 2. 500 ppb of bismuth chloride was also dissolved in this solution. Each colloidal solution was then subjected to stripping voltammetry as in the previous examples, rotating the GC electrode at 3000 rpm and applying a potential of −1.75 volt to this electrode during an accumulation stage of 120 seconds. As shown in FIG. 14 current peaks attributed to ZnS, CdS and PbS were observed at approximately −1.02 volt, −0.72 volt and −0.52 volt (relative to SCE) respectively and a current peak attributed to bismuth (chloride) is observed at approximately −0.14 volt. It can be seen that each peak is discrete, and there is no overlapping of redox signals. Thus, each species yields a voltammetric response that is identifiable and discrete, even in the presence of the other redox active species.
Example 7
Aliquots of a stock colloidal solution of PbS nanoparticles were progressively added to formation brine (composition as in Example 2) which also contained 500 ppb bismuth chloride. The solution was subjected to stripping voltammetry using the same conditions as in the previous Example after each addition of nanoparticles. Even at the lowest concentration, which was 60 ppb, there was a clear peak current in the voltammogram showing that PbS nanoparticles are detectable at this low concentration. The stripping peak current increased after each addition of nanoparticles. FIG. 15 is a plot of peak current (after subtracting baseline current) against PbS concentration, showing that the current is proportional to PbS concentration. The same procedure was carried out with CdS nanoparticles, showing them to be detectable at 30 ppb and also with ZnS nanoparticles showing them to be detectable at 130 ppb.
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In an arrangement for monitoring of flow within a hydrocarbon well or reservoir by means of one or more tracers which are placed at subterranean locations such that they may be present in flow produced from the well, the analysis of the flow produced from the well is carried out using an electrochemical method, preferably voltammetry, to detect tracer chosen to undergo a detectable electrochemical reaction. The tracer may be provided as nanoparticles in the well fluid.
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RELATED APPLICATION DATA
This patent is related to, claims priority benefit of, and is a U.S. National Phase Application of International Application No. PCT/EP2005/010947, which was filed on Oct. 21, 2005, and which claimed priority benefit of a German National Patent Application filed on Oct. 21, 2004, each of which is incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
The invention concerns a three-dimensional star-shaped decorative article or decorative object, especially for use as a Christmas window decoration or Christmas tree ornament, consisting of two or more blanks made of a paper or foil material, joined together, as well as a method and a set of blanks for its manufacture.
BACKGROUND OF THE INVENTION
Three-dimensional stars for decoration purposes during the Advent or Christmas season or as window decoration or Christmas tree ornament, produced by folding from paper blanks, are known, for example, a star marketed under the name of “Annaberg Window Star” [Annaberger Fensterstere] or “Erzgebirg Window Star” [“Erzgebirgischer Fensterstern”] with eight closed points extending in a circle over a middle part. There, on opposite sides of the star, the paper or foil material is provided with sixteen radially-extending fold lines, whereby it is folded in a V-shape in opposite directions at neighboring fold lines. By means of this alternating folding, areas that are folded inwardly are formed between two fold lines running through the tips of neighboring points, through the middle of which a fold line extends to a re-entering corner between the two neighboring points. Conversely, the fold lines that run from the middle of each side of the star to two neighboring re-entering corners define outwardly-folded areas through the middle of which the fold lines extend to the points of the star. Similar known stars with points extending outwards radially in several directions, known under the name of “Herrenhut star” are known from DE 36 18 092 A1, from DE 90 11 320 U1, from DE 85 16 185 U1 or from DE 196 09 168 C2. However, to produce these stars, several blanks and/or parts must be glued together, which is only possible manually, at a relatively high cost.
Furthermore, it is known from the origami technique that two-dimensional and three-dimensional stars with a different number of points can be produced from several paper blanks merely by folding. In order to achieve the holding together of the individual blanks without glue, normally a pocket is folded into each blank into which a part of a neighboring blank is inserted and this is also relatively costly and time-consuming.
Furthermore, a decorative Christmas star is disclosed in DE 1 735 277 U1. This folded star consists of two identical folded foil blanks joined together, each of which has a middle part as well as four longer and four shorter points extending outwardly beyond the middle part. Each blank is provided with eight fold lines which run from the midpoints of their middle parts to the tips of the points. The two blanks are folded in a V-shape alternately in opposite directions at the fold lines and then brought together in such a way that the midpoints of their middle parts point in opposite directions and the points are rotated by 45 degrees so that the shorter points of one blank come to lie in the recesses formed by the longer points of the other blank, wherein a mutual fixation on the blanks occurs that is not described in more detail.
Based on this, the task of the invention is to provide an aesthetically pleasing star-shaped three-dimensional decorative article from two or more blanks joined together, made of a paper or foil material, as well as to provide a method and a set of blanks for its production, making it possible to produce the decorative article without gluing and at a low cost.
SUMMARY OF THE INVENTION
This task is solved by the invention according to the features of the disclosed decorative object.
Surprisingly, it was found that a decorative object with features as disclosed herein makes it possible to assemble two or more blanks without glue to form a stable three-dimensional star, which has an essentially closed body and points that extend wreathlike beyond the body.
The decorative article according to the invention can be used for purposes other than advent or Christmas decorations, for example as a lampshade or packaging container.
At least one of the blanks must be star-shaped and have a middle part, several points extending beyond this outwardly and a plurality of fold lines that run from a point in the middle of the middle part in the direction of the points, so that the blank can be folded along neighboring fold lines alternately in opposite directions into a V-shape, whereby in each case, between two fold lines, separated by an additional fold line, inwardly-folded and outwardly-folded areas respectively are formed, with the additional fold line in their middle. When only two blanks are used, the other, preferably also star-shaped blank can be flat and can have all the openings required for joining the blanks. Since, however, these blanks have a very appealing three-dimensional form only when viewed from one of their sides, and therefore are mostly used as wall or table decoration, a preferred embodiment of the invention provides that the second blank has a form similar to or preferably identical to the said first blank, through which the production of the folded star can also be simplified. Then the middle part of the second blank also has several fold lines, running from a midpoint in the direction of the points and is folded alternately in opposite directions at neighboring fold lines. In order to join the two blanks, in this case the points on the inwardly-folded areas of one of the blanks are introduced through openings in the outwardly-folded areas of the other blank, as a result of which the folded star assumes an appealing three-dimensional form when viewed from either side.
The through openings in the blank or blanks are expediently designed in such a way that they have a rotational symmetry with respect to the midpoint of the particular blank. When using two blanks that are provided with fold lines or that are folded, with alternating longer and shorter points, the through openings are preferably arranged in the longer points, whereby their distance from the midpoint is preferably smaller than the distance from the tips of the shorter points and larger than the latter's distance from the re-entering corners between the points.
When three or more blanks are used, preferably two of the blanks are folded along the fold lines alternately in opposite directions in a V-shape, while the other blank or blanks are expediently essentially flat and are sandwiched between the folded blanks, whereby the openings for the inwardly-folded regions of the folded blanks are stamped out either in one or both of the flat blanks and/or in the other folded blank.
For better explanation, within the framework of this application, an “inwardly” or “outwardly” folded area of a blank of the finished three-dimensional decorative article is understood to be an area consisting of two neighboring slanting flanks of the blank, which always extend on both sides of a fold line to the respective neighboring fold line. Hereby, the middle fold line, which divides the area into two halves, forms the bottom line of a valley which has an approximately V-shaped cross-section, or the vertex line of a peak, which has an approximately V-shaped cross-section, whereby the outsides of the two flanks enclose an angle of less than 180 degrees in the first case and an angle of more than 180 degrees in the second case. Where neighboring fold lines, according to a preferred embodiment of the invention, run from the midpoint of each blank to the tips of neighboring points, each of the inwardly-folded or outwardly-folded areas respectively extends between one fold line and the fold line after the next one. The directional statements “inwardly” or “outwardly” refer to the already folded blank, namely when looking at their raised sides, the middle parts of which, in the finished three-dimensional decorative article, form the outside of the decorative article, which will also be referred to below simply as folded star.
Since the inwardly-folded and outwardly-folded areas follow each other alternately around the midpoint of each blank that is provided with fold lines, preferably each of the outwardly-folded areas of each blank is provided with a through opening and each of the inwardly-folded areas is provided with a point, which is introduced through a through opening in the opposing outwardly-folded area of the other blank, in order to join the two blanks by interleaving with one another.
When, during the manufacture of the folded star, the two blanks become somewhat compressed, when a part of their point is being introduced into the through openings of the other blank, and are, as a result, somewhat more strongly folded than before, due to the inherent elasticity of the paper or foil material, subsequently the blank has the tendency to return to a flatter, less strongly folded form. This counteracts an undesired separation of the two blanks, which are joined together, and leads to a more solid seating of the points in the through openings, especially when the opening cross-section of the latter ones corresponds approximately to the profile of the former ones. When during handling of the star pressing forces are applied onto the blanks from the outside, the latter ones spread out again, whereby the points penetrate further into the openings and thus the undesired separation of the blanks is similarly counteracted.
To prevent an unintended separation of the blanks, even when opposing tensile forces are applied to these, according to a preferred embodiment of the invention, it is provided that at least some of the points are interlocked with the other blank when inserted into the through openings, so that the points can no longer come loose from the through openings on their own. Preferably, the interlocking is achieved by providing at least some of the points with a notch on the inwardly-folded areas of each blank on one or both side edges of the points, the notch holding expediently an opposing end of the opening. However, alternatively, the openings can also be stamped out so that one or several projections extend beyond one of their opposite bordering edges, these projections being bent over, when a point is introduced, and penetrates into an opening stamped out from this point when the point has been inserted into the opening as far as prescribed.
Preferably, the openings are essentially in the form of V-shaped slit openings, which are stamped out expediently near a baseline which interconnects re-entering corners on both sides of the point. In the blanks provided with fold lines, expediently, an opening is stamped out only in every other point, whereby, in the case of blanks with alternating shorter and longer points, the opening is arranged in the respective longer points or in an adjoining area of the middle part bordering it, while the respective shorter point is inserted with its tip through a through opening in the other blank.
In order to facilitate the insertion of the points into the slit openings, their opposite bordering edges, over the entire length or over a part of the length of the openings, can have a small distance that is expediently two to ten times the thickness of the blank. The slit openings are preferably symmetrical with respect to the fold lines at the vertex lines of the outwardly-folded areas. Preferably, hereby, at least one of the two opposite bordering edges, expediently the outer bordering edge of each slit opening, is composed of two edge sections that converge in a V-shape in the direction of the fold line. The angle between the converging edge sections corresponds expediently to the angle of the cross-sectional profile of the point of the other blank inserted through the slit opening. In order to prevent a tearing of the slit openings at their ends, these latter ones can be rounded or provided with small rounded extensions.
The thickness of the finished folded star, that is, the mutual distance of the midpoints of the two blanks, can be altered while keeping the shape of the points essentially the same, by shifting the openings either closer to the midpoint of each blank, as a result of which the stars become thicker, or by shifting them further toward the tips of the points, as a result of which the stars become thinner. As already mentioned, the openings are preferably arranged near the foot of each point, that is, near the baseline which interconnects two neighboring re-entering corners on both sides of the respective point.
In order to insure that the middle parts of the two blanks surround an essentially completely closed cavity, another preferred embodiment of the invention provides that the two blanks lie against one another at their re-entering corners between neighboring points. Moreover, the opposite edges of each point entering through an opening are preferably formed between the ends of this opening and the two re-entering corners adjoining the point in such a way that they correspond there to the cross-sectional form of the outwardly-folded area provided with the opening. In this case, the two blanks are in line contact not only within the openings but also on both sides of them. Such a peripheral line contact between the two blanks can be achieved especially well in the case of triangular points when, on the inwardly-folded areas in the area of their foot, the points are somewhat narrower than or, as a maximum, exactly as wide as the points on the outwardly-folded areas of each blank, which are provided with openings.
In any case, for aesthetic reasons, it may be preferable to leave gaps between the blanks in order to achieve light-and-shadow effects or to create light exit openings for a light source arranged inside the star.
The folded star according to the invention can be varied in many other ways as well, for example with regard to material, which can be tinted cardboard or transparent, translucent or opaque plastic film, but can consist alternatively of multilayer glued colored transparent Chinese paper or a metal foil; the material thickness or area weight respectively, of the blanks, which are preferably in the range of 0.25 mm to 2 mm or 50 g/m 2 to 400 g/m 2 , depending on the material; the surface properties of the visible surfaces of the star, which can be smooth, rough or embossed; possible coatings on all or a part of the surfaces, for example glitter, metallization, gold or silver spray; breakthroughs or perforations in the blanks; as well as, naturally, the three-dimensional shape of the star, which can be adapted to satisfy almost any taste by changing the number of points, for example 6, 8, 10, 12, etc., the length of the points, the arrangement of longer and shorter points or differing lengths of the longer points, the projecting length of the shorter points, the shape of the individual points, for example with straight, zig-zag or wavy edges or double tips on all or a part of the points, the proportions of the star, that is, the thickness-to-length ratio of the points, as well as the size of the star.
Preferably, the fold lines extend from the midpoint of the middle part to the tips of the points, however, they can also end closer to the midpoint, for example at the foot of the points or at the openings, as a result of which, especially in the area of the points instead of the V-shaped cross-sections, U-shaped cross-sections result. Expediently, the fold lines are directed radially, but they can also be bent in a slightly spiral form. In case of points with double tips, the fold lines can end between the two tips. Generally, within the framework of the present invention, the fold line is understood to mean a line that facilitates the folding of the blanks and it is preferably an embossed groove or a row of perforations.
Furthermore, two blanks of different color or blanks with differently-colored flat surfaces can be used, as a result of which, in the former case, looking at it from one side, points arranged next to one another have different colors, while in the latter case additionally the colored stars themselves have different colors when looked at them from the opposite sides. When a transparent film material is used, the fold lines facing away from the user can be seen through the other blank, by means of which the three-dimensional effect can be further enhanced. Furthermore, especially for the blanks of larger folded stars, a translucent material can also be used and a light source can be placed inside the folded star, which illuminates both middle parts from the inside. Especially beautiful lighting effects can be achieved when the two blanks do not lie tightly against one another near the through openings or if the points introduced through the through openings are provided with small cut-outs or perforations in front of the through openings. Then the light from the inside of the folded star can fall through the gap between the blanks or through the cut-outs or perforations onto the tips of the other blank neighboring the openings and can illuminate these from the outside while the rest of the folded star emits light from within.
Expediently, the light source is an incandescent light bulb connected to a power source through at least one cable, which is led out from the inside of the folded star expediently in the area of two neighboring re-entering corners of the two blanks, and which can also be used to hang the folded star. Furthermore, the folded stars according to the invention can also be applied around the incandescent lights of a string of lights. Hereby, one can use a cable of the string of lights for hanging, guiding it inside the star between two neighboring points and leading it out again from it between two other neighboring points. Alternatively, one of the blanks can have an opening in the middle for a light socket of the incandescent light which is plugged into a mounting of the light through the opening, whereby the blank is clamped in-between the socket and the mounting.
An especially interesting appearance of the folded star is obtained also when all or part of the points are folded reversed in the outwardly-folded areas on the far side of the openings, so that at least some of the openings are adjoined by an outwardly-folded area on their inner bordering edges and by an inwardly-folded tip of the point at their outer bordering edges. The outwardly-folded areas on the inner side of each opening and the inwardly-folded tips on their outside are joined hereby expediently by two thin material bridges preferably bordering the ends of the openings. Using such an arrangement, the introduction of the points into the openings can also be facilitated during the assembly of the two blanks because the openings will open fairly wide in this way without having an adverse influence on the holding together of the finished folded star.
The hanging of the folded star is preferably carried out with the aid of a loop of thread that is preferably attached to one of the longer points provided with an opening, whereby, expediently, either it is glued onto the inwardly-folded side of its tip or it is threaded through two round openings connected to the side edges of the blank by cut-outs.
In order to produce the decorative article according to the invention, at first two or three blanks are stamped out from a paper or foil material, of which at least one has a middle part, a plurality of points extending beyond the middle part and a number of fold lines, preferably corresponding to the number of points, the fold lines running from a midpoint of the middle part outwardly in the direction of the points, so that, after stamping out, this blank can be folded at adjacent fold lines in a V-shape in opposite directions. Hereby, between each two fold lines separated by another fold line, inwardly-folded and outwardly-folded areas respectively are formed, with the other fold line in the middle. At least one of the other blanks is provided with a number of through openings in the stamping out process, through which the tips of the points of the folded blank can be inserted or introduced in order to join the two blanks with each other. Preferably, two identical blanks are used, both of which are provided with shorter points at the inwardly-folded areas and with longer points at the outwardly-folded areas and in which through openings are stamped out along the fold lines to the tips of the longer points, through which through openings the points at the inwardly-folded areas of the other blank can be inserted in order to join the two blanks with each other.
In machine production, this last step is preferably performed simultaneously for all points inserted through an opening, by first bringing both blanks into a position in which the points at the inwardly-folded areas of each blank face the openings in the outwardly-folded areas of the other blank, before moving them towards one another along a straight line running through their midpoints, whereby first the points enter into the through openings and then, by means of a further approach, the blanks become somewhat spread out in order to anchor the points in the openings.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be explained below with a few practical examples shown in the drawing. The following are shown:
FIG. 1 is a front view of an eight-point folded star according to the invention;
FIG. 2 is a view from the back of the folded star from FIG. 1 ;
FIG. 3 is a view of the folded star from FIG. 1 at a slant from front and above
FIG. 4 is a side view of the folded star from FIG. 1 ;
FIG. 5 is a sectional view of the folded star of FIG. 1 without hanger along the line V-V in FIG. 1 ;
FIG. 6 is a top view onto a blank for the two halves of the folded star from FIG. 1
FIG. 7 is a side view of a first variation of the folded star;
FIG. 8 is a front view of another variation of the folded star;
FIG. 9 is a front view of a ten-point folded star;
FIG. 10 is a front view of a six-point folded star;
FIG. 11 is a top view onto a blank for the two halves of the folded star from FIG. 10 ;
FIG. 12 is a partially cut-away front view of the folded star from FIGS. 1 to 5 with illumination;
FIG. 13 is a front view of a folded star made from a folded blank provided with fold lines and a flat blank;
FIG. 14 is a perspective side view of the folded star from FIG. 13 ;
FIG. 15 is a view from the back of the folded star from FIG. 13 ;
FIG. 16 is a top view onto the blank, provided with fold lines, of the folded star from FIGS. 13 to 16 ;
FIG. 17 is a top view onto the flat blank of the folded star from FIGS. 13 to 16 ;
FIG. 18 is a sectional view of the folded star from FIGS. 1 to 5 with illumination.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The folded stars 2 shown in FIG. 1 to 12 consist of two identical blanks 4 , 6 stamped out from cardboard or plastic film, folded and then assembled together, as well as of a loop made of thread 7 serving as hanger.
As depicted best in FIG. 6 based on the example of blank 4 , each of the two blanks 4 , 6 of the folded star 2 shown in FIGS. 1 to 5 has the shape of a flat eight-point star with four smaller points 8 and four larger points 10 , which project outward beyond an eight-cornered middle part 12 and which are delineated each by two straight converging side edges 14 and 16 , respectively. The middle part 12 is bordered toward the outside by imaginary baselines 18 , 20 , which, at the foot of each point 8 , 10 connect the two re-entering corners 22 bordering the points 8 , 10 , as it is shown in FIG. 6 by the dash-dot lines.
When the blanks 4 , 6 are stamped out of tinted cardboard or printed cardboard, this expediently has an area weight of at least 100 g/m 2 , better still more than 120 g/m 2 and best of all more than 130 g/m 2 , in order to obtain a finished folded star 2 with sufficient stiffness. When using colored or printed plastic film, depending on the size of the star, this has a thickness of at least 0.1 mm, better still at least 0.2 mm and best of all at least 0.25 mm.
Already during stamping, the blanks 4 , 6 are provided with a total of four embossed, pressed or perforated straight fold lines 24 , which each connect the tips of two opposite points 8 , 10 with one another and all of which intersect in the middle of middle part 12 at a point 26 . Moreover, during the stamping out, each of blanks 4 , 6 is provided with four slit openings 28 that are arranged near the baseline 20 of each larger point 10 , whereby they are oriented essentially transversely to the fold lines 24 running from the midpoint 26 to the tips of the larger points 10 and are symmetrical to the fold lines 24 . In the blank 4 shown in FIG. 6 , at their outer side facing the tips of points 10 , the slit openings 28 have a straight bordering edge 30 lying on the baseline 20 , while the bordering edge 32 on the inner side of the slit openings 28 is composed of two halves or edge sections which diverge outwardly at an obtuse angle. Alternatively, also both bordering edges 30 , 32 can have diverging edge sections. The outer bordering edges 30 of slit openings 28 are at a distance from midpoint 26 that is smaller than the distance between the midpoint 26 and a point P 1 on the fold lines 24 of the smaller points 8 , at which the width of the smaller points 8 corresponds approximately to the width of the slit openings 28 . In order to prevent a future tearing of the cardboard or of the plastic film, at the ends of slit openings 28 , these ends can be provided with small circular extensions 36 , as is indicated in a somewhat enlarged form at one of the slit openings 28 in FIG. 6 .
During the folding of blanks 4 , 6 following the stamping out, these are nicked or folded along the fold lines 24 between the tips of the larger points 10 in one direction and along the fold lines 24 between the tips of the smaller points 8 in the opposite direction, so that upon looking at them in the peripheral direction along baselines 18 , 20 , a flat, zig-zag shaped folding is obtained.
If one looks at the raised surface of a folded blank 4 , 6 , which, in the area of the middle part 12 , forms the subsequent outside of the folded star 2 , then each of the fold lines 24 between the tip of a larger point 10 and the midpoint 26 forms the vertex line 38 of an outwardly-folded area 40 . This outwardly-folded area 40 consists of two slanting flanks adjoining each other along the vertex line 38 , extending from there to the respective neighboring fold line 24 and forming a peak with a V-shaped cross-section, whereby their outsides enclose an angle of more than 180 degrees. Conversely, each of the fold lines 24 between the tip of a smaller point 8 and the midpoint 26 , when viewed from the subsequent outside of the folded star 2 , forms the bottom line 42 of an inwardly-folded area 44 , which is composed of two slanted flanks adjoining each other along bottom line 42 and which extend from the bottom line 42 to the respective neighboring vertex line 38 and form a valley with a V-shaped cross-section, whereby their outsides enclose an angle of less than 180 degrees. Each of the two flanks of the outwardly-folded areas 40 at the same time forms a flank of an inwardly-folded area 44 neighboring it in the clockwise or counterclockwise direction. In other words, the fold lines 24 meeting at midpoint 26 delineate pairwise areas 40 , 44 having V-shaped cross-sections that are folded inwardly and outwardly, alternately.
Next, the two folded blanks 4 , 6 are aligned so that, first of all, the midpoints 26 of their middle parts 12 point in opposite directions and lie on a common straight line, which is perpendicular to the planes defined by the tips of the longer points 10 or by the tips of the shorter points 8 or by the re-entering corners 22 between points 8 , 10 , respectively, and that, secondly, opposite each larger point 10 of a blank 4 , there is a smaller point 8 of the other blank 6 ; that is, the two blanks 4 , 6 are rotated by 45 degrees with respect to one another around the straight line through the midpoints 26 . Furthermore, the two blanks 4 , 6 are briefly folded more strongly by reducing the angle between the outsides of the flanks of the inwardly-folded areas 44 , until the tips of the smaller points 8 of each blank 4 , 6 are positioned accurately opposite from the middle of the slit openings 28 of the respective other blank, 6 , 4 . This is always possible, at least when the midpoint angles between two neighboring fold lines 24 of the blanks 4 , 6 are all the same and the tips of the smaller points 8 as well as the centers of the slit openings 28 lie on the fold lines 24 .
Then the two blanks 4 , 6 are moved towards each other along the straight lines through the midpoints 26 of their middle parts 12 until the smaller points 8 enter with their tips into the slit openings 28 of the larger points 10 and penetrate into these simultaneously until their side edges 14 , which diverge toward the middle part 12 , contact the ends of the slit openings 28 . Then the two blanks 4 , 6 are slightly spread out by enlargement of the angle between the outsides of the flanks of the inwardly-folded areas 44 , while the smaller points 8 penetrate further into the slit openings 28 until they project a little distance with their tips beyond the other blank 6 , 4 on the opposite side of the folded star 2 . The spreading of the blanks 4 , 6 leads to a mutual interleaving thereof because hereby the distance between the tips of the smaller points 8 and the straight line through the midpoints 26 of the middle parts 12 of the two blanks 4 , 6 increases faster than the distance between this straight line and the slit openings 28 in the outwardly-folded areas 40 .
When, during transportation or handling, pressing forces are applied to the middle parts of the two blanks 4 , 6 of the completed folded star 2 , this also leads to the spreading of the blanks 4 , 6 , through which, the smaller points 8 , to the extent it is still possible, move a few millimeters further into the slit openings 28 . Therefore, the holding together of the two blanks 4 , 6 is not harmed by the pressing forces, but, on the contrary, it is improved. If a pressing force is applied to a smaller point 8 that projects through a slit opening 28 , due to the interleaving of the blanks 4 , 6 at the other points 8 , 10 , this does not lead to the exit of the point 8 from the slit opening 28 either. However, if the need arises, the two blanks 4 , 6 of the folded star 2 can be separated by gripping them in the area of their middle parts 12 and pulling them apart. However, this can also be prevented by assuring that upon introduction of the points 8 into the slit openings 28 , these interlock with the latter. For this purpose, the smaller points 8 are provided with small notches or cut-outs 48 on their opposite side edges 14 , as shown in FIG. 6 . With these notches or cut-outs 48 , the opposite ends of the slit openings 28 engage when the points 8 are introduced as far as possible into the slit openings 28 . The notches or cut-outs 48 are arranged in a region of the points 8 where these have essentially the same width as the slit openings 28 . The notches or cut-outs 48 are designed so that, together with the side edges 14 of the points 8 , they form small barbs 50 , which can interlock at the ends of the slit openings 28 . Entry of these barbs 50 through the slit openings 28 when the respecting point 8 is introduced is achieved due to the fact that the point 8 deforms somewhat in the slit opening 28 .
After the joining of the two blanks 4 , 6 , their middle parts 12 enclose a cavity 52 ( FIG. 5 ) in the form of a polyhedron, which has almost closed peripheral contacting lines, due to a mutual contact of the two blanks 4 , 6 , on both sides of each slit opening 28 and in the region of the re-entering corners 22 , when the blanks 4 , 6 have approximately the sizes or size relationships shown in the drawing. In these blanks 4 , 6 , the smaller points 8 at the inwardly-folded areas 44 , are, on the one hand, shorter and in the area of their baseline 18 somewhat narrower than the larger points 10 at the outwardly-folded areas 40 . On the other hand, their side edges 14 are approximately in alignment with bottom lines 20 of the adjoining larger points 10 . Thus the side edges 14 of the smaller points 8 and the baselines 20 of the larger points 10 approximately delineate a polygon in which the number of corners corresponds to half of the number of points 8 , 10 of the blanks 4 , 6 . However, by changing the dimensions of the larger or longer and of the smaller or shorter points 8 , 10 , respectively, that is, their width and length as well as their relationships of length to breadth, folding stars 2 can also be produced in which the blanks 4 , 6 do not lie against one another on either side of the slit openings 28 or do so only in sections.
Moreover, the tips of the V-shape-folded shorter points 8 of each blank 4 , 6 extend through the slit openings 28 in the longer points 10 , whereby on the opposite side of the folded star 2 they project slightly beyond the outwardly-folded areas 44 of the respective other blank 6 , 4 , which have a V-shape cross-section. However, in comparison to the longer points 10 , they are visually less pronounced, so that when viewing the front or back of the folded star 2 , an impression of an eight-pointed star is obtained, as shown in FIG. 1 and FIG. 2 .
However, if desired, the size of the projection of points 8 beyond the slit openings 28 can be enlarged by the lengthening and narrowing of the shorter points 8 to such an extent that, on the other side of the slit openings 28 , these will have the same or similar length as the other points 10 , through which, at least when viewed from the side, the impression of a folded star 2 with a larger number of points 8 , 10 is obtained, as shown in FIG. 7 . The thickness of the folded star 2 , that is, the distance between the midpoints 26 of the middle part 12 of the two blanks 4 , 6 , can be changed too, for example by placing the slit openings at a smaller or larger distance from the midpoint 28 . Especially well-proportioned flat three-dimensional folded stars 2 are obtained when the slit openings 28 are arranged somewhat radially outwardly from the bottom lines 20 of the larger points 10 .
Furthermore, the folded star 2 can be provided with a larger or smaller number of larger and smaller points 8 , 10 by providing the blanks 4 , 6 with a total of ten or twelve points 8 , 10 or any arbitrary even number of points 8 , 10 , instead of four larger points 10 and four shorter points 8 , and by joining these together in the manner described above. A folded star 2 produced in this way with a total of ten longer points 10 is shown in FIG. 9 , while FIG. 10 shows a six-point folded star 2 with six longer points 10 and FIG. 11 shows one of the two identical blanks 58 , 60 used for producing the folded star 2 shown in FIG. 10 .
Apart from a different number of longer points 10 and shorter points 8 , the folded star 2 shown in FIG. 10 also exhibits a few other smaller differences in comparison to the folded star 2 shown in FIGS. 1 to 5 . First of all, in the case of the folded star 2 from FIG. 10 , the blanks 58 , 60 along each fold line 24 running diagonally through their midpoint 26 , are not folded in a single direction, but in one direction along one half of the fold line 24 and in the opposite direction along the other half of the fold line 24 , that is, on the other side of midpoint 26 , so that an inwardly-folded area 44 lies diagonally across from an outwardly-folded area 40 and not an outwardly-folded area 40 as in the folded star 2 from FIGS. 1 to 5 . Secondly, the longer points 10 of blanks 58 , 60 , provided with the slit openings 28 , have at their baseline 20 two cut-outs 62 open at the edges, these extending from opposite side edges 16 of the points 10 along the baseline 20 a short distance in the direction of the neighboring front ends of the slit openings 28 . When joining the two blanks 58 , 60 , these cut-outs 62 can engage in each case with a corresponding cut-out 62 of the other blank 60 , 58 , which, in the completed folded star 2 , leads to a mutual overlapping of the side edges 16 of neighboring points 10 and thus it has a somewhat different appearance as a consequence. However, on the other hand, this measure also has the effect that the two blanks 58 , 60 lie more tightly against each other along their peripheral contacting line and due to the additional interleaving in the area of the cut-outs 62 will be held together even stronger. A similar result is achieved when the points 10 are provided with a cut-out 62 only at one of their side edges 16 , which then must be arranged on the same side of all points 10 .
When the cut-outs 62 are extended to the vicinity of the opposite front ends of the slit openings 28 , as it is shown in the case of the eight-point folded star 2 in FIG. 8 , the tips of the larger points 10 can be turned down or reversely folded on the other side of the slit openings 28 along their fold lines 24 . Then the two flanks of the points 10 form an inwardly-folded area 44 on the other side of slit openings 28 , which is connected through two narrow material bridges 64 between the front ends of slit openings 28 and the ends of the cut-outs 62 with which an outwardly-folded area 40 on this side of slit openings 28 is connected. In this way, using simple means, a significantly different appearance can be produced in the perspective view (not shown).
In contrast to the folded stars 2 described above, which consist of two identical blanks 4 , 6 , each provided with fold lines 24 , one of the two blanks 66 of the folded star 2 represented in FIGS. 13 to 15 is flat, as shown in FIG. 17 , whereby it has a total of eight equal-sized triangular points 68 arranged at the same angular distances and projecting radially beyond a middle part 12 and the same number of equal-sized V-shaped slit openings 70 , which are each located at the transition between one of the points 68 and the flat middle part 12 of blank 66 with no fold lines. As shown in FIG. 16 , the other blank 72 has eight longer points 74 and eight shorter points 76 which alternate in the peripheral direction and are also arranged at the same angular distances. Apart from the fact that the number of points 74 , 76 is larger than the number of points 8 , 10 in the blanks 4 , 6 ; 58 , 60 described before, the blank 72 differs from these only in the fact that it has no slit opening, since these are all stamped out from the other blank 66 . While the tips of the shorter points 76 arranged on the inwardly-folded areas 44 of this blank 72 are inserted through the slit openings 70 of the flat blank 66 and project beyond its bottom side, the longer points 74 with their tips project radially to the outside in the intermediate spaces between two adjacent points 68 of the flat blank 66 , as is shown best in FIGS. 14 to 16 . When viewing in the direction of the arrow in FIG. 14 , thus one obtains the impression of a sixteen-point folded star with a raised middle part 12 having eight points 74 and eight flat points 68 which are arranged in the intermediate spaces between the points 74 .
As can be seen best in FIG. 17 , the outer bordering edges 78 of the slit openings 70 of the flat blank 64 each consist of two halves or edge sections converging in a V-shape. The length of the two edge sections and the angle enclosed by them are preferably chosen so that the outer bordering edges 78 of the slit openings 70 of blank 66 , after the joining of the two blanks 66 , 72 along their entire length, lie against the flanks of the inwardly-folded areas 44 of the other blank 72 and are in alignment with the side edges 16 of the longer points converging toward the tips, as is shown best in FIG. 14 . By changing the distance of the slit openings 70 from the midpoint 26 of the blank 66 , the size of the projecting length of the folded blank 72 beyond the plane of blank 66 can be altered. If desired, in addition the contrast between the flat blank 66 and the raised folded blank 72 can be enhanced or emphasized by applying a different color to the blanks 66 , 72 .
Furthermore, the folded stars 2 shown in FIG. 1 to 11 can be equipped with an additional flat blank (not shown) which is sandwiched between the two folded blanks 4 , 6 ; 58 , 60 . The additional blank, like the blank 66 in FIG. 17 , is provided with slit openings, through which all or a part of the shorter points 8 at the inwardly-folded areas 44 of the two other blanks 4 , 6 ; 58 , 60 are inserted with their tips. The shorter points 8 can each be additionally introduced through a slit opening 28 in the respective other folded blank 6 , 4 ; 60 , 58 or can be anchored only in the additional flat blank, whereby this blank then holds together the two folded blanks 4 , 6 ; 58 , 60 . The flat blank subdivides the cavity 52 defined by the middle parts 12 of the blanks 4 , 6 ; 58 , 60 into two halves. However, it can have an opening in the middle in case such a subdivision is not desired.
The loops of thread 7 which serve to hang the folded stars 2 and which are shown only in the case of the folded star 2 in the figures, can be glued on the folded star 2 with their thread ends next to one another using an adhesive, preferably a hot melt adhesive, as shown in FIG. 2 . Alternatively, however, the loop of thread 7 can also extend through a small round opening (not shown) in one or both blanks 4 , 6 . The attachment of the loop of thread is done expediently either in the middle of a larger point 10 or in the middle between two larger points 10 .
In order to facilitate the attachment of the loop of thread 7 , this can also extend through a V-shaped cut-out symmetrically to fold line 38 , converging toward middle part 12 , in one of the larger points 10 .
The folded stars 2 can be made in different sizes and are used preferably for Advent or Christmas decoration, for example as window stars or as tree ornaments for a Christmas tree, but also as lanterns, as lampshades for light fixtures or as packaging containers, for example for the packaging of small objects, such as jewelry. Furthermore, a plurality of the folded stars 2 can be lined up along a string of lights, whereby the lights are arranged inside the folded stars 2 . When the folded stars 2 are made of a weather-resistant material, trees or shrubs in gardens or parks can, for example, be decorated with illuminated folded stars 2 lined up on a string of lights.
FIG. 12 shows a single folded star 2 of such a string of lights, which is made of a transparent paper or foil material. The light arranged inside it in the form of an electrical incandescent light 80 is connected through two cables 82 to a power source (not shown). The cables 82 each enter into the cavity 52 enclosed by the middle parts 12 of the blanks 4 , 6 , between two opposing re-entering corners 22 of the two blanks 4 , 6 , and serve at the same time for hanging the folded stars 2 of the string of lights so that loops of thread can be omitted here. Alternatively, the folded star 2 shown in FIG. 12 can also be hung as an illuminated solitary light on a single two-line cable (not shown).
FIG. 18 shows another possibility of the combination of a folded star 2 with an electrical incandescent light 80 of a commercial string of lights. One of the blanks 4 of the folded star has there in the middle part 12 a circular opening 84 concentric to its midpoint 26 for a socket 86 for an incandescent bulb 88 of the light 80 , which, after entering through the opening 84 , is inserted in the known manner into a complementary lamp mounting 90 connected to the cable 82 , in order to clamp the edge of the opening 84 between the socket 86 and the mounting 90 before the two blanks 4 , 6 are connected to one another. In order to support the attachment of the blank 4 between the socket 86 and the mounting 90 , instead of the stamped round opening 84 , one can also stamp radial cuts starting from the midpoint 26 with a length corresponding to the radius of the opening 84 in blank 4 . In this case, the triangular sections formed between the cuts are bent to the outside of the blank 4 , and when the socket 86 is inserted into the mounting 90 they are firmly secured between these two (not shown).
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The invention relates to a star-shaped decorative object ( 2 ), in addition to blanks and an associated production method. The decorative object comprises at least two interconnected blanks ( 4, 6; 58, 60; 66, 72 ) consisting of paper or foil, at least one ( 4, 6; 58, 60; 72 ) of which comprises a central part ( 12 ) and a plurality of points ( 8, 10; 74, 76 ) projecting outwards beyond the central part ( 12 ). The central part ( 12 ) of said blank ( 4, 6; 58, 60; 72 ) is provided with several fold lines ( 24 ) that run from a central point ( 26 ) towards the points ( 8, 10; 74, 76 ) and is folded alternately along adjoining fold lines ( 24 ) in opposite directions in a V, in such a way that between two respective fold lines ( 24 ) that are separated by an additional fold line ( 24 ), areas ( 44 and 40 ) that are folded inwards and outwards are formed with the additional fold line ( 24 ) running through their center. To interconnect the two blanks ( 4, 6; 58, 60; 66, 72 ) to form a hollow three-dimensional body, the points ( 8 ) are pushed through openings ( 28; 70 ) of one of the other blanks ( 6, 4; 60, 58; 66 ) in areas of the folded blank ( 4, 6; 58, 60; 72 ) that are folded inwards ( 44 ).
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RELATED APPLICATIONS
[0001] Copending U.S. patent applications Ser. Nos. 09/614,399; 09/680,796, and 09/750,954 filed Jul. 12, 2000; Oct. 6, 2000; and Dec. 28, 2000 respectively are related to the present invention and are herein incorporated by reference in their entireties.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an incentive based method to attract potential consumers to a sales agent for presentation of a sales pitch for a good or service.
[0004] 2. Description of the Related Art
[0005] Internet commerce has exploded into the public awareness. The 1990s and first part of 2000 saw a flurry of activity in the industry as the “dot coms” advertised in such diverse locations as the Super Bowl, on the sides of buses, at trade shows, and the like. The initial burst of energy and investment focused on the Business to Consumer model.
[0006] These days, market evolutionary forces are winnowing out companies with poorly designed web pages. Other companies that do have a viable good or service and have a viable business model are also struggling to secure new customers. Some statistics show that an online broker spends as much as three hundred dollars to attract a new account. This is an incredibly daunting figure for a new company to spend for each new customer.
[0007] At the same time, it is becoming increasingly hard to get new customers to new sites. People are becoming sedentary in their online shopping, only going to a few established Internet commerce providers. This may be in spite of the fact that other sites have better prices, better service, and/or better products.
[0008] Thus, there remains a need for a method to attract people to interface with a business on a personal level so as to promote the creation of a new customer account and/or sale to the new customer.
SUMMARY OF THE INVENTION
[0009] The present invention comprises distributing computer readable media to a plurality of potential consumers. Upon installation of a computer readable medium into the potential consumers' computers, a software program stored on the medium reviews the hardware configuration of the potential consumer. Depending on the hardware available, and specifically on the presence or absence of a network connection, the software program may launch a game locally or take the potential consumer to a URL where the potential consumer may play a game.
[0010] The game may award the potential consumer a prize related to a business that is seeking to attract new consumers. To collect the prize, the potential consumer is connected to a sales agent who may then make a sales presentation to the potential consumer personally.
[0011] In one embodiment, where there is no network connection on the computer, the potential consumer may telephone the sales agent. In another embodiment, where there is a network connection, the potential consumer is taken to a web site at which the sales agent and the potential consumer may begin a dialogue. The dialogue format depends on the nature of the hardware available at the potential consumer's computer. The format may be a text based chat session, a voice over Internet session, or a full duplex video conference, or other format, as needed or desired.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] [0012]FIG. 1 illustrates a front plan view of a computer such as may be used by a potential consumer using the present invention;
[0013] [0013]FIG. 2 illustrates a schematic diagram of one embodiment of a network via which the potential consumer may be connected to a remote sales agent;
[0014] [0014]FIG. 3 is a flow chart illustrating exemplary preliminary steps taken by a business to utilize the present invention; and
[0015] [0015]FIGS. 4A & 4B are a flow chart illustrating exemplary steps taken by the potential consumer and software of the present invention separated due to space constraints.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The present invention comprises a method to attract potential consumers in hopes that they will consummate a sale with a business. A potential consumer, as that term is used herein, may be anyone capable of entering into a legal contract. A business, as that term is used herein, may be a corporation, a partnership, a sole proprietorship, or other real or legal entity that conducts a legal business. The following businesses are particularly contemplated as being well suited for using the present invention: pornographers, electronic product sales, psychic hotlines, online trading companies, and telemarketers for various goods and services.
[0017] The present invention assumes that the business has the means to handle incoming phone calls and communications in an appropriate manner. Particularly contemplated are the call centers described in the previously incorporated related applications. The entity that runs the call center is sometimes referred to herein as the service provider. These call centers enable sales agents to handle incoming bi-directional video calls as well as push content down transmission paths to potential consumers. Content and communication may be text based, such as by an instant messenger program, voice over Internet, or full video streaming as needed or desired. The interested readers are referred to the previously incorporated applications for a full explanation of these features. However, a brief overview of some of the hardware is presented with reference to FIGS. 1 and 2.
[0018] To effectuate the present method, it is advantageous for the potential consumer to have some sort of data processing device such as a computer 10 , illustrated in FIG. 1. It is expected that the methodology of the present invention will be implemented at least in part by software that will run, in part, on the computer 10 . Computer 10 may comprise a display 12 , a desk unit 14 housing a motherboard and microcontroller such as an INTEL PENTIUM IV or the like, a keyboard 16 , a mouse 18 , a microphone 20 , a speaker 22 , and other paraphernalia as is well understood. Further, the desk unit 14 may comprise a floppy disc drive 24 and a CD-drive 26 capable of receiving computer readable media such as a disk 28 and a CD 30 respectively. The relevant portions of the software of the present invention may be stored on the computer readable media 28 , 30 as needed or desired.
[0019] A plurality of computers 10 operate within a communication system 100 as illustrated in FIG. 2. In particular, computers 10 may be part of a managed portal network 102 operated by a service provider operating according to the present invention, although this need not be true. Managed portal network 102 interfaces with the Internet 104 and particularly with the World Wide Web (www). It is more likely, however, that the computers 10 are not part of the managed portal network 102 , and merely connected to the Internet 104 such as through an Internet Service Provider (ISP) such as Time Warner's Roadrunner service, aol.com, Bellsouth.net, or the like. A call center is also associated with the managed portal network 102 . This call center may be comparable to that disclosed in the above identified related applications. Alternatively, the call center may be comparable to that disclosed in U.S. Pat. No. 6,046,762, the entire disclosure of which is hereby incorporated by reference. A brief overview of an appropriate system is herein provided to avoid the need to read those references. However, the interested reader is encouraged to read the references for a complete and full understanding of the call center. A message connection server 106 , which may double as an Internet connection server, an agent interaction server 108 , and an ACD server 110 may also form part of the managed portal network 102 . Further, aplurality of customer service representative (CSR) stations 120 and supervisor stations 122 may be included within the managed portal network 102 . Still further, a commerce server 130 may be part of the managed portal network 102 . It should be appreciated that the communicative links between elements of the managed portal network 102 are high bandwidth, high speed connections such as T 1 lines, E 1 lines, broadband wireless links, two-way satellite communication, cable lines, fiber optic lines, or the like. However, data compression technology allows normal phone lines or twisted pair lines to be used if required.
[0020] Servers 106 , 108 , and 110 act to route messages from computers 10 to CSR stations 120 and to the commerce server 130 as needed. CSR stations 120 comprise a camera (not shown explicitly), at least one monitor, a headset having a microphone and speaker capabilities, and other communicative capabilities. Each CSR station 120 is staffed by a trained sales agent having one or more specialty areas. As calls come in to the server 106 , the server 106 routes the call to the appropriate CSR station 120 . The accessed CSR station 120 may then begin bi-directional, interactive communication with the computer 10 . This interactive communication may take the form of a video phone call, content being pushed down the communicative link, or other form as needed or desired and as explained fully in the above incorporated co -pending applications. The term call, as used herein, specifically includes accessing a web page, making a phone call, or the like.
[0021] There are several ways that the present invention may be practiced. An exemplary technique is herein presented. Referring to FIG. 3, a flow chart illustrates some preliminary steps that a business may undertake to practice the present invention more effectively. In particular, the business secures some form of mailing list of potential consumers (block 210 ). This mailing list may be purchased from another entity such as a telephone company, a credit card company, or the like as needed or desired. This mailing list may alternatively be self-generated by employees or independent contractors as needed or desired. Still other techniques of securing mailing lists are well understood in the art. This mailing list may include a potential consumer's residence or postal address, a telephone number associated with the potential consumer, an email address, and other information as needed or desired. Note that not all the information listed need be present in the mailing list, but the list at a minimum should have enough information about a potential consumer through which to contact the potential consumer by some medium.
[0022] The business then identifies a good and/or service to be promoted by the present invention (block 212 ). The range of available goods and/or services that may be effectively promoted with the present invention is essentially limitless, although the present invention is particularly well suited for reasonably sophisticated goods and/or services such as home electronics, Internet trading services, and the like. The mailing list may be screened for certain demographics if that information is available based on the good and/or service promoted. For example, individuals below a certain income threshold may be excluded as unlikely to be able to afford a particular good and/or service. As another example, individuals in a certain postal area may not be able to receive satellite television service as a result of nearby geographical features, and thus they may be excluded from a promotion for satellite television. Other thresholds or filters will be readily apparent to those designing the promotions, as the business presumably knows a target audience for its good/service.
[0023] The business may then create a prize schedule to go with the promotion (block 214 ). The prize schedule may ensure a minimum participatory prize with multiple levels of awards above that. For example, in a promotion to sell satellite television sets and service, the business may decide that everyone who participates may receive a free installation. Some percentage of participants will receive a free satellite dish and installation. Some other, smaller percentage of participants will receive a small cash prize. Finally, a very small percentage of participants in the promotion will receive a large cash prize.
[0024] The business may select a game and coordinate the game with the prize schedule (block 216 ). For example, a slot machine type game may be selected and the prizes assigned to permutations on the results of the slot wheels. In this way, odds may be created that the correct percentages will be awarded the desired number of prizes. Other games and prize schedules are also contemplated.
[0025] The business may generate the code for the game (block 218 ). This may be as simple as adapting an existing game for use with the prize schedule or writing the code from scratch, but the end result is the creation of software to run the game. The software may be imprinted on computer readable media such as compact discs, diskettes, memory sticks, smart cards, or the like as needed or desired. The code may be in any suitable programming language such as C++, visual basic, or the like.
[0026] The business may then distribute copies of the game (block 220 ). In a first embodiment, the distribution is through the mail system. The distribution may be accompanied by the appropriate disclaimers that no purchase is necessary to play, void where prohibited, and the like to comply with the appropriate gaming laws of the jurisdictions in which the game will be played.
[0027] In a second embodiment, the distribution is not a distribution of tangible computer readable media, but rather an electronic distribution, such as by email, or delivered wirelessly to a mobile terminal such as a mobile phone, personal digital assistant, or the like. Thus, mailing lists that include phone addresses or email addresses are also useful to the business. In this embodiment, having acquired the potential consumer's email account, the service provider may generate low cost, mass email. While indiscriminately sent email is not always appreciated by the recipients, it is possible that the service provider may target the recipients to those who have indicated a willingness to receive promotional offers or the like. The software may be sent as an attachment to the email, or in the body of the email. Attachments such as .docs, .mp 3 s, .jpgs, and the like are well understood and most conventional mail servers have the ability to attach and decipher files. In this particular case, th e attachment may be an executable file, and thus may be rigorously vetted against viruses and the like to instill consumer confidence.
[0028] As still another embodiment, the computer readable media may be passed out at a high traffic location, such as a kiosk in a mall, on an airport concourse, or other place as needed or desired. It should be appreciated that in this embodiment, it is not necessary to secure a mailing list.
[0029] It should be appreciated that the computer readable media may be packaged in eye catching, motivational materials so that potential consumers are encouraged to install the software on their computer 10 from the computer readable media.
[0030] Note that the precise order of the steps in FIG. 3 may be rearranged as needed by the business. For example, the game design and prize schedule need not occur after securing the mailing list.
[0031] Taking the embodiment where the potential consumer receives a tangible computer readable medium, the next steps in the process are illustrated in FIGS. 4A & 4B. This is the same flow chart, however, it has been broken apart for clarity. The process starts at block 250 and the potential consumer (labeled user in FIGS. 4A & 4B) inserts the medium into the computer 10 (block 252 ). Depending on the nature of the media, this may be the floppy drive 24 or the CD drive 26 . The software on the medium performs a system check of the computer 10 into which it has been inserted (block 254 ). This may be done during an installation process or otherwise hidden from the potential consumer's awareness if needed or desired.
[0032] The system check determines several things, but initially determines if there is a modem or other network interface card (NIC) present in the computer 10 (block 256 ). If the answer to block 256 is negative, the software immediately presents the game to the potential consumer (block 258 ). In an exemplary embodiment, the game is a slot machine game run on the potential consumer's computer 10 . The game runs and the potential consumer is awarded a prize determined by the prize schedule. The potential consumer is presented some interface displaying a phone number and/or other contact information of a sales agent or the like (block 260 ). The interface may further explicate that the prize is only redeemable if the potential consumer contacts the sales agent. The process ends (block 265 ). This is for situations in which the potential consumer does not have a modem or other outside Internet access mechanism installed in his comp uter 10 . The potential consumer would call a sales agent in the call center previously described and collect the prize while being exposed to a sales presentation.
[0033] If the answer to block 256 is yes, there is a modem or NIC, then the system check continues (see FIG. 4B). Note that the system check may check for cable modems, DSL modems, a T 1 connection, other conventional modems, Ethernet connections, or the like as needed or desired. The modem may also be wireless if needed or desired, but the purpose of the test is to determine if the potential consumer has access to the Internet 104 for the purposes explained below.
[0034] The next test the system check runs is to determine if the computer 10 has a sound card (block 270 ). If the answer is yes, the system check determines if there is a video card (block 272 ). If the answer is yes, the system check determines if there is video conferencing software such as MICROSOFT NETMEETING™ (block 274 ). Finally, the system check determines if there is a video camera installed on the computer 10 (block 276 ).
[0035] Having made the appropriate determinations, the software then connects to the Internet 104 . This may launch a web browser such as NETSCAPE NAVIGATOR™, MICROSOFT INTERNET EXPLORER™, or other browser as needed or desired. Further, if the potential consumer does not have a normal Internet Service Provider (ISP), the software may summon a routine that calls a toll free number for an ISP belonging to the business. Other techniques of securing an Internet connection will be readily apparent to those skilled in the art. Once the Internet connection is secured, the software takes the browser to a web page that prompts the user for additional information (block 278 ).
[0036] If at any time in the system check steps 270 - 276 the answer is no, the system check skips to block 278 . This order may be changed, but by placing steps 270 - 276 in this order, processing steps are minimized if a negative result is returned. This is because it will not matter if there is a video card if there is no sound card, and similarly, it will not matter if there is video conferencing software if there is no sound card or no video card. The system check also outputs the results of each check (noted data results in FIG. 4B) that is sent to the sales agent (block 280 ).
[0037] The additional information that the web page in block 278 asks for may include whether the potential consumer has a microphone 20 and speakers 22 on their computer 10 (block 282 ). It may further ask what sort of connection the potential consumer has with the Internet 104 (block 284 ). The potential consumer may answer with a baud rate, ( 56 . 6 , 48 . 8 , etc.) DSL modem, cable modem, T 1 , or the like. The potential consumer is also prompted for a name, a phone number, and any other additional hardware that may be of interest (block 286 ). Note that the prompts for the information may be in conventional data field entry screens, by check boxes, radio buttons, or the like as needed or desired. The data results of blocks 282 - 286 are also sent to the sales agent (block 280 ).
[0038] After determination of the hardware, both from the system check and the potential consumer's input, the software may query the potential consumer as to how they wish to proceed if there is not a microphone 20 and/or speakers 22 present (block 288 ). This may be done in a new web page as needed or desired. The game is presented to the potential consumer (block 290 ). The potential consumer plays the game and is alerted to the existence of the prize that they have won (block 292 ).
[0039] The potential consumer is then connected to a sales agent in the call center (block 294 ) and the sales agent is given the opportunity to solicit and consummate a sale with the potential consumer. This opportunity to make such a sales presentation may comprise the sales agent using the tools of the call center to present a full bi-directional video communication with the potential consumer as explicated in the previously incorporated applications. Alternatively, if the potential consumer does not have the tools for such a video conference, or the bandwidth connection to support a lot of video streaming supplemental information (or other reason), the sales agent may proceed with a voice over Internet communication, a text based message connection such as an instant messenger program, or other communication technique as needed or desired. The process then ends (block 265 ).
[0040] In another embodiment, a virtual sales agent may be presented to the potential consumer. Rather than have a video feed from the sales agent, a “talking head” such as those created by LIPSinc of Research Triangle Park, North Carolina may be used. Further information about such virtual personalities may be found at www.lipsinc.com. The virtual agent may be controlled by the sales agent as needed or desired.
[0041] Note that the connection to the Internet 104 may occur after the game is played if needed or desired. Thus, the game, system check, and consumer inputs as to hardware configurations may all be based on the software present on the computer readable medium. Other rearrangements in the precise order of the events in FIGS. 4A & 4B are also contemplated. For example, the potential consumer input as to the existence of speakers 22 and a microphone 20 may occur after the game is played. Such variations are well within the scope of the present invention.
[0042] In an alternate embodiment, the software is not stored on a computer readable medium, but rather may be delivered to the computer 10 through some other technique such as email, wireless transmission or the like. As yet another variant, the software may be a JAVA applet and act like a pop up window when the potential consumer performs a predetermined action while surfing the web. For example, leaving a certain site may trigger a pop up window that runs the software of the present invention and gives the potential consumer the opportunity to play the game and ultimately be subjected to the sales presentation of the sales agent.
[0043] As still another embodiment, it is possible to install the software on computers prior to delivering the computers to the purchaser. Thus, for example, an individual may enter a computer store, purchase a computer, take it home, and upon turning on the computer, the individual is presented with an icon on the desktop or other appropriate start mechanism to launch the software of the present invention. This may provide out of-the-box live customer support. This may help ensure proper installation or the sale of additional peripheral items such as printers, scanners, internet subscriptions, and the like. The icon may remain for further customer support if needed or desired.
[0044] Note that in this last embodiment it may not be appropriate to require the consumer to play a game, especially when they are seeking customer support. This situation is also within the scope of the present invention. However, the ability to interact personally with a live sales agent has heretofore not been provided for new computer users or those seeking customer support.
[0045] The present invention may, of course, be carried out in other specific ways than those herein set forth without departing from the scope and the essential characteristics of the invention. The present embodiments are therefore to be construed in all aspects as illustrative and not restrictive and all changes coming within the meaning and equivalency range of the appended claims are intended to be embraced therein.
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A method of promoting sales for goods and/or services comprises providing a potential consumer a software program that enables the potential consumer to play a game. To collect the prize of the game, the potential consumer may contact a remote sales agent, subjecting the potential consumer to a sales presentation.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The field of the present invention is that of optical systems used in the transmission and/or amplification of optical signals.
2. Description of the Prior Art
Systems of the above kind conventionally include a few hundred or a few thousand kilometers of transmission optical fibers, depending on the application, divided into sections connected by repeaters in which the optical signals transmitted are amplified and sometimes reshaped. Optical signals are transmitted in fibers simultaneously on a plurality of optical channels. The signals are therefore not all subjected to the same optical treatment and stresses. The optical repeaters therefore include different optical modules for processing some or all of the transmitted signals. For example, a repeater can include amplifiers (fiber amplifiers or semiconductor amplifiers), chromatic dispersion compensators, gain equalizers, multiplexers and any other module that the person skilled in the art may deem to be required.
Transmission optical fibers generally have a monomode or multimode core for the simultaneous propagation of a plurality of optical signals surrounded by a cladding protected by a polymer coating. The core and/or the cladding can be of silica or of a polymer plastics material, depending on the application. The fibers have a signal attenuation and a pass-band suited to the applications in which they are used.
An optical repeater generally includes two stages of optical amplifiers, and often a gain equalizer, multiplexer, dispersion compensator or other optical module between the two stages. These modules introduce losses, which can generally reach 9 dB, and their parameters are generally set by a specification during design and installation of the transmission line.
Optical systems are often subject to change and it is not uncommon for the parameters of an optical module no longer to be suitable for current transmission spectra. For example, the various optical components constituting the modules are subject to aging, localized work may be carried out on the line, or optical transmission channels or modules may be added after the line is installed. The parameters of the modules previously set then become unsuitable.
Moreover, fiber amplifiers (erbium-doped fiber or Raman amplifiers) are associated with pump lasers whose performance is fixed once they are installed. Just like pump lasers, amplifiers are often standardized and are not necessarily well matched to the operating conditions under which they are used, and even more so to changes therein.
Moreover, optical amplifiers are often associated with gain equalizers for compensating amplification differences between the transmitted signal channels. The equalizers are designed to conform to operating conditions of the amplifier that depend among other things on the input power. The input power may vary along the transmission line, for example as a function of the length of fiber through which the signal has traveled. A variation of power at the input of an amplifier shifts its operating point and causes a mismatch of the associated equalizer filter. For this reason dynamic optical equalizers have been developed; they adapt to the operating conditions of the amplifiers at all points of the transmission line. Gain equalizers provide a dynamically adjustable attenuation as a function of wavelength.
It is therefore standard practice to provide adjustable modules in optical repeaters, in particular dynamic optical equalizer modules, to adjust the operating conditions of the optical modules along the transmission line. Similarly, using tunable pump lasers to modify the characteristics of the amplifiers of an optical system is also known in the art.
Adjustable modules of the above kind (and lasers) exist already and are well known to the person skilled in the art. The essential problem is that of controlling the adjustable modules to modify their parameters in order to select optimum operating conditions. Tunability may be provided at the level of the module or at the level of the optical component.
Existing control techniques necessitate the measurement of certain optical or performance parameters and applying appropriate control signals as a function of the measured parameters.
FIG. 1 relates to a first prior art control technique and shows diagrammatically a repeater 10 with two amplifier stages 3 and 4 and an optical module 5 , for example a gain equalizer. An optical measurement is carried out, for example by means of an optical spectrum analyzer 7 such as an OPM (optical power monitor) or an OCM (optical channel monitor). The transmission spectrum can be measured optically before, after or between the amplifier stages 3 and 4 . The measurement is fed back to a control unit, such as a local processor, which operates on the module 5 or directly on the optical component to adjust it as a function of fixed parameters, such as a gain template in the case of a gain equalizer module. This prior art technique necessitates measuring means 7 (for example a spectrum analyzer) for each repeater 10 , which represents a non-negligible cost, and does not necessarily produce the optimum adjustment because it does not reflect all of the optical changes to the line, the template set for a given component not necessarily being the optimum at a given time. This control technique takes no account of the possibility of disturbances farther down the line.
FIG. 2 relates to another prior art control technique, and shows the same components identified by the same reference numbers. This prior art technique measures optical parameters at a given point of the line for action upstream thereof. For example, the adjustment of a given optical module 5 located in a given optical repeater 10 is controlled by a measurement effected by a spectrum analyzer 7 in a downstream repeater 10 ′ which is around ten repeaters farther along, for example. The adjustment control signal is then transmitted by supervisory channels CS in the transmission line which are reserved for control and command purposes and can be used for the above measurements and adjustments.
The above kind of technique reflects the actual transmission line constraints better, but is relatively greedy in terms of capacity. The supervisory channels are limited so as not to encroach on the wanted bandwidth and are essentially reserved for purposes other than optical module adjustment.
Moreover, the above control techniques are still based on the replication of optical parameters, such as a power spectral template or an optical signal to noise ratio (OSNR) template, which have a direct influence on the quality of the signal but which are defined on the basis of hypotheses that cannot generally be guaranteed throughout the life of a system, or even when it is installed.
The document EP0700178 discloses a method of adjusting a wavelength tunable source and filters in an optical system having a single transmission channel, the method including:
a step of measuring the quality of the optical signal at the output of the system as defined by an error function based on the eye diagram or the bit error rate (BER), a step of sweeping the wavelength to adjust it for an expected reduction of the error function, and a step of adjusting transmission characteristics of the filter as a function of the chosen wavelength.
To be more precise, the evolution of the error function as a function of wavelength is completely characterized throughout the range of values thereof.
This method is not compatible with optimizing the performance of the system in operation, i.e. while the system is transmitting data, as it necessarily implies momentarily degraded performance.
The method disclosed in the above prior art document is not a reliable and powerful method of adjusting a dynamic module.
Moreover, the above method relates to the adjustment of parameters associated with only a single transmission channel, rather than relating more widely to selective adjustment of parameters of one channel as a function of other channels.
Moreover, all the control techniques previously described are unable to adjust a plurality of parameters of a plurality of remote optical modules as a function of each other to optimize the operation of the optical system as a whole, in particular if there is a large number of parameters and/or a large number of transmission channels and/or of modules.
Accordingly, the above technique cannot efficiently manage dynamic modules distributed along a transmission line. Transmission system performance could therefore be significantly improved by efficient dynamic control of optical modules distributed along a transmission line.
The object of the present invention is to propose a new technique for dynamically controlling one or more optical modules included in an optical system including a plurality of transmission channels on the basis of the optical signal at the output of the system for adjustment of optical parameters of one or more upstream adjustable modules, which adjustment is optimized in terms of efficiency (response time, output signal quality improvement, reliability, etc.).
In particular, the invention aims to adjust optical parameters of the modules distributed within a system, such as a transmission line, as a function of each other and on the basis of the optical signal at the output of the system.
SUMMARY OF THE INVENTION
To this end the present invention proposes a method of dynamically adjusting an optical module in an optical system including a plurality of transmission channels, which method includes the following steps:
measuring the quality of the optical signal at the output of the system as defined by an error function; varying an optical parameter of at least one module of the system; measuring a differential error introduced by each variation on the error function of the optical signal at the output of the system; estimating an operating point of the system corresponding to an expected reduction of the error function; and adjusting a parameter of an optical module toward the operating point of the system.
Each parameter variation is advantageously effected in the vicinity of the value of the parameter associated with a current operating point and is preferably an infinitesimal variation.
According to one feature of the invention, two or more parameters of an optical module of the system are successively affected by a variation.
According to one feature of the invention, all parameters of each optical module of the system are successively affected by a variation.
According to one feature of the invention, the steps of the method are repeated in looped fashion during operation of the optical system.
In the various embodiments of the invention the quality of the optical signal for each transmission channel at the output of the system is measured by a forward error correction module on the basis of a bit error rate or by means of an eye diagram.
The error function used to define the quality of the optical signal at the system output is defined as the sum of the bit error rates squared E=(Σ i BER i 2 ) for all the transmission channels of the system or is of the type E=[αΣ(ei) β ] γ where ei is the quality of the i th transmission channel of the system and α, β and γ are positive constants and are not necessarily integers.
In an advantageous embodiment of the invention the operating point is calculated by a central control unit of the system and the variations of the parameters of the optical modules and the commands for adjusting each optical module of the system are determined by a central control unit of the system and transmitted over supervisory channels of the system.
In an advantageous embodiment of the invention the optical modules to be adjusted are modeled and a function is defined for direct conversion between a command sent by the supervisory system and the variation induced in an optical parameter of the module and the conversion is preferably effected by the module itself so as to produce a given parameter variation in response to a given received command.
The present invention also provides an optical system including a plurality of transmission channels and adjustable optical modules and means for implementing a method of dynamically adjusting an optical module in an optical system including a plurality of transmission channels, which method includes the following steps:
measuring the quality of the optical signal at the output of the system as defined by an error function; varying an optical parameter of at least one module of the system; measuring a differential error introduced by each variation on the error function of the optical signal at the output of the system; estimating an operating point of the system corresponding to an expected reduction of the error function; and adjusting a parameter of an optical module toward the operating point of the system.
According to one feature of the invention, the optical system further includes means for varying optical parameters of each module associated with means for measuring differential errors introduced by the variations on an error function representing the quality of the optical signal at the output of the system and means for calculating an operating point of the system corresponding to a reduction of the error function.
Depending on the intended application of the invention, the adjustable optical modules are optical gain equalizers and/or pump lasers and/or multiplexers and/or couplers and/or chromatic dispersion compensators and/or polarization mode dispersion compensators and/or filters and/or variable attenuators and/or variable slope attenuators and/or selectors (add and drop multiplexers (OADM) or cross connect selectors (OXC)).
The features and advantages of the present invention will become more clearly apparent after reading the following description, which is given by way of illustrative and nonlimiting example and with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 , already described, shows diagrammatically a first prior art control technique.
FIG. 2 , already described, shows diagrammatically a second prior art control technique.
FIG. 3 shows diagrammatically an optical module control technique according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 3 , the technique of controlling adjustable optical modules of an optical system including a plurality of transmission channels is based on measuring the quality of the optical signal at the output of the system for a plurality of channels. Accordingly, a global analysis can be carried out and the adjustment of the parameters of each module can take account of general system constraints. This kind of global analysis implies taking account of all elements of the transmission line, from end to end, and means that all sources of deterioration are taken into consideration.
The system concerned can be a transmission line including sections of transmission fiber connected by optical repeaters 10 . However, the method according to the invention applies equally to other optical systems, such as branched or meshed transparent optical networks including nodes including in particular optical selectors, couplers or multiplexers, for example.
According to the invention, the optical quality of the signal received at the output is measured by a measuring unit 8 such as an electronic signal processor unit. Depending on the embodiment, the quality measurement can be derived from an eye diagram representing the quality of the optical transitions between 0 bits and 1 bits of the received optical signals or the bit error rate (BER). Some optical systems process the BER to provide error correction feedback, known as forward error correction (FEC). A forward error correction module FEC is provided in the receiver of the optical system. The FEC module detects errors with a high success rate (typically one error in 100 000 is not detected).
To this end, some transmission channels and/or some time slots of each channel are dedicated to control bits such as parity bits, for example. The bit error rate BER prior to correction by the FEC module is a parameter that is directly accessible in conventional optical systems, with an uncertainty in respect of the BER as estimated by the FEC module that is very low, typically of the order of 10 −5 .
Starting from a given operating point of the optical system referred to as the current operating point X, an adjustable module X 1 of an optical module of the system is disturbed successively by a variation ΔX 1 in the vicinity of the value of said parameter associated with the current operating point, preferably an infinitesimal variation, whereas all the other parameters of the system are maintained at their value X k (k≠1) corresponding to the current operating point X. Similarly, one or more other adjustable parameters X 1 of an optical module of the system are successively disturbed with a similar variation ΔX 1 whereas all the other parameters of the system are maintained at their value X k (k≠1) corresponding to the current operating point X.
This can advantageously apply to all parameters of all modules.
The variations are advantageously transmitted to the modules via the supervisory channels and commanded by a central supervisory unit CPU of the system that is also able to interpret the measurements of the quality of the signal at the output of the system. A scalar error function is calculated from these basic measurements on each transmission channel i.
A differential error ΔE( 1 )=(δE/δX 1 ) X ΔX 1 in the quality of the signal E at the output introduced by each variation is then measured, the differential error being negative (representing an improvement in operating conditions) or positive (representing a deterioration of operating conditions). For example, an error function defined as the sum of the BER squared E=(Σ i BER i 2 ), accentuating the weights of the most effective channels, is considered to constitute a good estimate of the error at a given time.
In one particular embodiment, the error function used can be of the type E=[αΣ(ei) β ] γ , where ei is the quality of the i th transmission channel of the system, determined by the FEC module or from the eye diagram, and where α, β and γ are positive constants and not necessarily integers. It is preferable if β>1, 1.5<β<3, and γ=1/β.
The central control unit CPU of the system then calculates a new operating point of the system from each differential error introduced by each parameter variation. Note that a plurality of optical parameters X 1 can be relevant to variations for the same transmission channel i. Accordingly, a new operating point of the system can be determined that corresponds to an estimated reduction of the error function, the objective being to minimize the error function or at least to ensure that the function remains in the immediate vicinity of a minimum.
Accordingly, the new operating point calculated generally corresponds to a movement of the operating point in the direction of the gradient vector of the error function (ΔE/ΔX). The movement increment is determined by the optimization algorithm (i.e. the minimization of the error function) as a function of the amplitude of the gradient vector. The increment is generally reduced progressively to obtain effective minimization. However, the movement may be too great and lead to an increase in the error function, which will be corrected on the next movement. Suitable optimization algorithms, possibly with management of operating point movement, are well known to the person skilled in the art, and are described, for example, in “Numerical Recipes in C”, 3rd edition.
Each module 3 , 4 , 5 can then be tuned as a function of the parameters corresponding to the new optimum operating point X of the system. A given module may not be adjusted under its own optimum operating conditions, but is tuned for optimum operating conditions for the system as a whole to which it belongs.
Like the variations, the adjustments of optical parameters of each module are commanded by the central unit CPU and transmitted via the supervisory channels CS or by any other appropriate means. The supervisory channels of the system according to the invention are busied only for controlling the optical modules and not for forwarding information to the central unit from each module, which limits the required capacity, in terms of supervisory channel bandwidth, for implementing the control method according to the invention, and reduces the response time.
In an advantageous embodiment, a parameter variation (as defined above) is requested for a particular duration, so that it is not necessary to send commands to return that parameter to the value corresponding to the reference point. Also, it is not necessary to wait for the measurement of the quality of the signal corresponding to a given variation before commanding variation of the next parameter. A plurality of successive variations can be requested by means of a single command, especially if the variations concern different parameters of the same optical module.
A control method according to the invention does not require an accurate knowledge of the correspondence between control parameters (voltage, current, etc.) and the optical parameters for each module of a system. This leads to a reduction in production testing costs and widens the parameter tolerances, in particular with regard to aging, during optical module fabrication. It is also possible to use the method according to the invention to make good any unexpected drift of an optical system. The optical system measures directly the variation of the signal quality as a function of the applied command, and it is therefore not necessary to know the correspondence between the command and the optical function variation of each module. Approximate modeling of the optical module can nevertheless be beneficial for optimizing the search for the optimum operating point thanks to a reduced choice of parameters for the command. For example, a function can be defined for direct conversion between the command sent by the supervisory system and the induced variation of an optical parameter of a modeled module. The conversion can advantageously be effected by the module itself in order to limit the necessary calculations by the CPU and most importantly to avoid having to update an exhaustive list in the CPU of the optical modules and the associated mathematical models. Thus the CPU processes all the parameters indifferently.
A control method according to the invention can further extend the adjustment of parameters to optical modules other than equalizers, variable slope attenuators and variable attenuators, for example to amplifier pumps.
Moreover, the optical modules subject to dynamic control can be distributed all along the transmission system without impacting on control quality. In particular, this allows the use of a simplified dynamic equalizer which can be integrated into the optical amplifier or its pumping module in each repeater, instead of using a complex equalizer every five to ten repeaters.
This kind of technique for controlling the optical parameters of a system has an improved response time compared to the prior art techniques. Considering, for example, an optical system comprising an undersea optical link transmitting 160 channels at 10 Gbit/s over approximately 7 000 km with 200 optical repeaters, Raman distributed amplifiers with four pumps per repeater, and an equalizer with 40 adjustable parameters every ten repeaters, that amounts to 800 pumps and 400 equalization parameters, i.e. 1 200 parameters in total. Considering an acceptable maximum BER of 10 −5 , assessing the impact of each disturbance takes approximately 10 ms with a 0.1% accuracy for the BER of each channel. An additional 10 ms can advantageously be provided for stabilization of the system before the error introduced is estimated. Accordingly, with 20 ms for estimating the differential error for each parameter varied, 24 s are required to determine a new operating point of the system, which is perfectly acceptable for an undersea link, in which the time constants of optical parameter fluctuations generally correspond to hours or even days.
Similarly, considering, for example, an optical system comprising a terrestrial optical link transmitting 160 channels at 10 Gbit/s over approximately 2 000 km with 20 optical repeaters, amplifiers with 16 pumps per repeater, and an equalizer with 40 adjustable parameters every ten repeaters, that makes 320 pumps and 80 equalization parameters, i.e. 400 parameters in total. Taking again 20 ms as the time to estimate the differential error for each parameter varied, it takes 8 s to determine a new operating point of the system, which is perfectly acceptable for a terrestrial link.
In an emergency, if a sudden deterioration of signal quality is detected on one or more transmission channels, a fast estimate can be effected with a reduced number of parameters affecting the damaged channels directly and selectively. The central supervisory unit of the system can quickly determine the parameters to be tested and adjusted.
Similarly, in the event of intentional modification of the operation of the system, such as reconfiguration of an OADM or an OXC, the central unit can react quickly and selectively adjust the parameters directly affected, for example the power of the new channels added or adjacent channels.
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A method of dynamically adjusting an optical module in an optical system including a plurality of transmission channels includes the following steps: measuring the quality of the optical signal at the output of the system as defined by an error function, varying an optical parameter of at least one module of the system, measuring a differential error introduced by each variation on the error function of the optical signal at the output of the system, estimating an operating point of the system corresponding to an expected reduction of the error function, and adjusting a parameter of an optical module toward the operating point of the system.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims subject matter that is described in co-pending United States Patent Application filed simultaneously herewith and entitled “Nanostructured Battery Having End-Of-Life Cells,” Ser. No. ______ and United States Patent Application filed simultaneously herewith and entitled “Reserve Cell-Array Nanostructured Battery,” Ser. No. ______.
FIELD OF THE INVENTION
[0002] The present invention relates generally to batteries and, more particularly, to batteries having nanostructured surfaces.
BACKGROUND OF THE INVENTION
[0003] Many beneficial devices or structures in myriad applications rely on batteries as a power source. A typical liquid-cell battery, such as battery 101 in FIG. 1 , is characterized by an electrolyte liquid 102 which provides a mechanism for an electrical charge to flow in direction 103 between a positive electrode 104 and a negative electrode 105 . When such a battery 101 is inserted into an electrical circuit 106 with illustrative load 108 , it completes a loop which allows electrons to flow in direction 107 around the circuit 106 . The positive electrode 104 thus receives electrons from the external circuit 106 . These electrons then react with the materials of the positive electrode 104 in reduction reactions that generate the flow of a charge to the negative electrode 105 via ions in the electrolyte liquid 102 . At the negative electrode 105 , oxidation reactions between the materials of the negative electrode 104 and the charge flowing through the electrolyte fluid 102 result in surplus electrons that are released to the external circuit 106 .
[0004] As the above process continues, the active materials of the positive and negative electrodes 104 and 105 , respectively, eventually become depleted and the reactions slow down until the battery is no longer capable of supplying electrons. At this point the battery is discharged. It is well known that, even when a liquid-cell battery is not inserted into an electrical circuit, there is often a low level reaction with the electrodes 104 and 105 that can eventually deplete the material of the electrodes. Thus, a battery can become depleted over a period of time even when it is not in active use in an electrical circuit. This period of time will vary depending on the electrolyte fluid used and the materials of the electrodes.
[0005] More recently, batteries having at least one nanostructured surface have been proposed wherein nanostructures are used to separate the electrolyte from the electrode until such a time that the battery is to be used. This is typically referred to as a reserve battery (as opposed to a primary battery that is manufactured with the electrolyte in contact with the electrodes of the battery). An example of the use of electrowetting principles applied to reserve batteries is described in copending U.S. patent application Ser. No. 10/716,084 filed Nov. 18, 2003 and entitled “Electrowetting Battery Having Nanostructured Surface,” which is hereby incorporated by reference herein in its entirety. As disclosed in the '084 application, when it is desired that the battery generate a current, the electrolyte is caused to penetrate the nanostructured surface and to come into contact with the electrode of the battery, thus resulting in the above-discussed flow of electrons around a circuit. Such a penetration of nanostructures is achieved, for example, by applying a voltage to the nanostructures such that the contact angle of the electrolyte relative to the nanostructured surface is decreased. When the contact angle is decreased, the electrolyte penetrates the nanostructures and is brought into contact with the electrode.
SUMMARY OF THE INVENTION
[0006] The present inventors have realized that, while prior reserve and primary batteries were useful in many regards, they were limited in certain aspects. In particular, once the batteries were manufactured and activated (in the case of a reserve battery), it was typically impossible to return the batteries to a reserve state (i.e, to separate the electrolyte from the battery electrodes).
[0007] Therefore, the present inventors have invented a small battery having a nanostructured battery electrode wherein it is possible to reverse the contact of the electrolyte with the battery electrode and, thus, to return a battery to a reserve state after it has been used to generate current. In order to achieve this reversibility, the nanostructures on the battery electrode comprise a plurality of closed cells and the pressure within the enclosed cells is varied. In a first embodiment, the pressure is varied by varying the temperature of a fluid within the cells by, for example, applying a voltage to electrodes disposed within said cells. In a second illustrative embodiment, once the battery has been fully discharged, the battery is recharged and then the electrolyte fluid is expelled from the cells in a way such that it is no longer in contact with the battery electrode.
BRIEF DESCRIPTION OF THE DRAWING
[0008] FIG. 1 shows a prior art liquid-cell battery as used in an electrical circuit;
[0009] FIG. 2 shows a prior art nanopost surface;
[0010] FIGS. 3A, 3B , 3 C, 3 D and 3 E show various prior art nanostructure feature patterns of predefined nanostructures that are suitable for use in the present invention;
[0011] FIG. 4 shows a more detailed view of the prior art nanostructure feature pattern of FIG. 3C ;
[0012] FIGS. 5A and 5B show a device in accordance with the principles of the present invention whereby electrowetting principles are used to cause a liquid droplet to penetrate a nanostructure feature pattern;
[0013] FIG. 6 shows the detail of an illustrative nanopost of the nanostructure feature pattern of FIGS. 5A and 5B ;
[0014] FIG. 7 shows an illustrative liquid-cell battery in accordance with the principles of the present invention wherein the electrolyte in the battery is separated from the negative electrode by nanostructures;
[0015] FIG. 8 shows the illustrative battery of FIG. 7 wherein the electrolyte in the battery is caused to penetrate the nanostructures and to thus contact the negative electrode; and
[0016] FIGS. 9A, 9B and 9 C show a battery with the principles of the present invention wherein a droplet of electrolyte is disposed in an initial position suspended on top of a nanostructured feature pattern ( FIG. 9A ), is caused to penetrate the feature pattern ( FIG. 9B ), and is then caused to return to a position suspended on top of the feature pattern ( FIG. 9C );
[0017] FIGS. 10A and 10B show an illustrative closed-cell structure in accordance with the principles of the present invention;
[0018] FIGS. 11A and 11B show the detail of one cell in the illustrative structure of FIGS. 10A and 10B ; and
[0019] FIGS. 12A, 12B and 12 C show a battery in accordance with the principles of the present invention wherein a droplet of electrolyte is disposed in an initial position suspended on top of a nanostructured feature pattern ( FIG. 12A ), is caused to penetrate the feature pattern ( FIG. 12B ), and is then caused to return to a position suspended on top of the feature pattern ( FIG. 12C ).
DETAILED DESCRIPTION
[0020] FIG. 2 shows an illustrative nanopost pattern 201 with each nanopost 209 having a diameter of less than 1 micrometer. While FIG. 2 shows nanoposts 209 formed in a somewhat conical shape, other shapes and sizes are also achievable. In fact, cylindrical nanopost arrays have been produced with each nanopost having a diameter of less than 10 nm. Specifically, FIGS. 3A-3E show different illustrative arrangements of nanoposts produced using various methods and further show that such various diameter nanoposts can be fashioned with different degrees of regularity. Moreover, these figures show that it is possible to produce nanoposts having various diameters separated by various distances. An illustrative method of producing nanoposts, found in U.S. Pat. No. 6,185,961, titled “Nanopost arrays and process for making same,” issued Feb. 13, 2001 to Tonucci, et al, is hereby incorporated by reference herein in its entirety. Nanoposts have been manufactured by various methods, such as by using a template to form the posts, by various means of lithography, and by various methods of etching.
[0021] FIG. 4 shows the illustrative known surface 401 of FIG. 3C with a nanostructure feature pattern of nanoposts 402 disposed on a substrate. Throughout the description herein, one skilled in the art will recognize that the same principles applied to the use of nanoposts or nanostructures can be equally applied to microposts or other larger features in a feature pattern. The surface 401 and the nanoposts 402 of FIG. 4 are, illustratively, made from silicon. The nanoposts 402 of FIG. 4 are illustratively approximately 350 nm in diameter, approximately 6 μm high and are spaced approximately 4 μm apart, center to center. It will be obvious to one skilled in the art that such arrays may be produced with regular spacing or, alternatively, with irregular spacing.
[0022] As typically defined a “nanostructure” is a predefined structure having at least one dimension of less than one micrometer and a “microstructure” is a predefined structure having at least one dimension of less than one millimeter. However, although the disclosed embodiments refer to nanostructures and nanostructured surfaces, it is intended by the present inventors, and will be clear to those skilled in the art, that microstructures may be substituted in many cases. Accordingly, the present inventors hereby define nanostructures to include both structures that have at least one dimension of less than one micrometer as well as those structures having at least one dimension less than one millimeter. The term “feature pattern” refers to either a pattern of microstructures or a pattern of nanostructures. Further, the terms “liquid,” “droplet,” and “liquid droplet” are used herein interchangeably. Each of those terms refers to a liquid or a portion of liquid, whether in droplet form or not.
[0023] In many applications, it is desirable to be able to control the penetration of a given liquid into a given nanostructured or microstructured surface and, thus, control the contact of the liquid with the underlying substrate supporting the nanostructures or microstructures. FIGS. 5A and 5B show one embodiment where electrowetting is used to control the penetration of a liquid into a nanostructured surface. Electrowetting principles and controlling the movement of a liquid across a nanostructured or microstructured surface are generally described in U.S. patent application Ser. No. 10/403,159 filed Mar. 31, 2003 and titled “Method And Apparatus For Variably Controlling The Movement Of A Liquid On A Nanostructured Surface,” which is hereby incorporated by reference herein in its entirety. As discussed previously, the general use of electrowetting principles in batteries is described in above-referenced copending U.S. patent application Ser. No. 10/716,084.
[0024] Referring to FIG. 5A , a droplet 501 of conducting liquid (such as an electrolyte solution in a liquid-cell battery) is disposed on nanostructure feature pattern of cylindrical nanoposts 502 , as described above, such that the surface tension of the droplet 501 results in the droplet being suspended on the upper portion of the nanoposts 502 . In this arrangement, the droplet only covers surface area f 1 of each nanopost and has a contact angle with each nanopost of, for example, θ 0 . The nanoposts 502 are supported by the surface of a conducting substrate 503 . Droplet 501 is illustratively electrically connected to substrate 503 via lead 504 having voltage source 505 . An illustrative nanopost is shown in greater detail in FIG. 6 . In that figure, nanopost 502 is electrically insulated from the liquid ( 501 in FIG. 5A ) by material 601 , such as an insulating layer of dielectric material. The nanopost is further separated from the liquid by a low surface energy material 602 , such as a well-known fluoro-polymer. Such a low surface energy material allows one to obtain an appropriate initial contact angle (i.e., θ 0 ) between the liquid and the surface of the nanopost. It will be obvious to one skilled in the art that, instead of using two separate layers of different material, a single layer of material that possesses sufficiently low surface energy and sufficiently high insulating properties could be used.
[0025] FIG. 5B shows that, by applying a low voltage (e.g., 10-20 volts) to the conducting droplet of liquid 501 , a voltage difference results between the liquid 501 and the nanoposts 502 . The contact angle between the liquid and the surface of the nanopost decreases and, at a sufficiently low contact angle, the droplet 501 moves down in the y-direction along the surface of the nanoposts 502 and penetrates the nanostructure feature pattern until it completely surrounds each of the nanoposts 502 and comes into contact with the upper surface of substrate 503 . In this configuration, the droplet covers surface area f 2 of each nanopost. Since f 2 >>f 1 , the overall contact area between the droplet 501 and the nanoposts 502 is relatively high such that the droplet 501 contacts the substrate 503 . One skilled in the art will recognize that other methods of causing the electrolyte to penetrate the nanostructures, such as decreasing the temperature of the electrodes, can be used. The present invention is intended to encompass any such method of causing such penetration.
[0026] FIG. 7 shows an illustrative battery 701 whereby an electrolyte fluid 702 is contained within a housing having containment walls 703 . The electrolyte fluid 702 is in contact with positive electrode 704 , but is separated from negative electrode 708 by nanostructured surface 707 . Nanostructured surface 707 may be the surface of the negative electrode or, alternatively, may be a surface bonded to the negative electrode. One skilled in the art will recognize that the nanostructured surface could also be used in association with the positive electrode with similarly advantageous results. In FIG. 7 , the electrolyte fluid is suspended on the tops of the nanoposts of the surface, similar to the droplet of FIG. 5A . The battery 701 is inserted, for example, into electrical circuit 705 having load 706 . When the electrolyte liquid 702 is not in contact with the negative electrode, there is substantially no reaction between the electrolyte and the electrodes 704 and 708 of the battery 701 . Accordingly, there is no depletion of the materials of the electrodes. Thus, it is possible to store the battery 701 for relatively long periods of time without the battery becoming discharged.
[0027] FIG. 8 shows the battery 701 of FIG. 7 inserted into electrical circuit 705 wherein, utilizing the electrowetting principles described above, a voltage is applied to the nanostructured surface 707 thus causing the electrolyte fluid 702 to penetrate the surface 707 and to come into electrical contact with the negative electrode 708 . One skilled in the art will recognize that this voltage can be generated from any number of sources such as, for example, by passing one or more pulses of RF energy through the battery. When the penetration of the electrolyte into the nanostructures occurs, electrons begin flowing in direction 801 through the circuit 705 , as described above, and the load 706 is powered. Thus, the embodiment of FIGS. 7 and 8 show how a battery can be stored without depletion for a relatively long period of time and can then be “turned on” at a desired point in time to power one or more electrical loads in an electrical circuit.
[0028] The battery described in FIGS. 7 and 8 is referred to as a reserve battery or, in other words, a battery that is manufactured with the electrolyte separated from at least one of the electrodes in the battery. Primary batteries, on the other hand, are batteries that are manufactured with the electrolyte in contact with the electrodes of the battery. As such, primary batteries are always undergoing oxidation reactions, even when not inserted in an electrical circuit. Therefore, primary batteries typically have a relatively short shelf-life relative to reserve batteries.
[0029] The present inventors have recognized that it would be desirable to be able to selectively turn on and off the generation of current in a battery. Such a capability would have many novel uses. For example, the battery could be turned on only when it was needed, thus preventing excess oxidation that could lead to premature discharge of the battery. Additionally, such a capability could lead to a new category of reserve rechargeable batteries that, once recharged, can be turned off. As is well-known, rechargeable batteries (also referred to herein as secondary batteries) are batteries in which the electrodes can be regenerated by reversing the current flow to and within the battery. While it is possible to recharge the reserve nanostructured batteries described previously, no effective methods have yet been realized for returning the recharged battery to a reserve state once it is recharged.
[0030] The present inventors have further realized that, in the nanostructured batteries discussed above herein, it would be desirable to reverse the penetration of the electrolyte in a way such that it is restored to its original reserve position suspended on the nanostructures above the electrode. Reversible penetration of nanostructured or microstructured surfaces by a droplet of liquid is the subject of copending U.S. patent application Ser. No. 10/674,448, filed Sep. 30, 2003 and entitled “Reversible Transitions On Dynamically Tunable Nanostructured Or Microstructured Surfaces,” which is hereby incorporated by reference herein in its entirety.
[0031] FIGS. 9A, 9B and 9 C illustrate a selective/reversible penetration of droplet 901 , which is illustratively a droplet of electrolyte such as electrolyte 702 in FIG. 7 into nanostructure pattern 904 . Specifically, FIG. 9A shows electrolyte droplet 901 disposed on a nanostructure or microstructure feature pattern 904 that is supported by substrate 905 (which is, illustratively, the electrode 503 in FIG. 5A ). Next, as shown in FIG. 9B and discussed above, droplet 901 is caused to penetrate the feature pattern 904 . Finally, as shown in FIG. 9C , it is desirable to reverse the penetration of droplet 902 . FIGS. 10A and 10B show, respectively, a three-dimensional view and a top cross-sectional view of an illustrative feature pattern in accordance with the principles of the present invention that is capable of accomplishing the reversible penetration shown in FIGS. 9A-9C . Specifically, in the present illustrative embodiment represented by FIGS. 10A and 10B , the feature pattern does not comprise a number of posts spaced a distance away from each other. Instead, a number of closed cells 1001 , here illustrative cells of a hexagonal cross section, are used. Each cell 1001 has an electrode 1002 disposed along the inner wall of the cell. As used herein, the term closed cell is defined as a cell that is enclosed on all sides except for the side upon which a liquid, such as an electrolyte liquid, is intended to be disposed. One skilled in the art will recognize that other, equally advantageous cell configurations and geometries are possible to achieve equally effective closed-cell arrangements. FIGS. 11A and 11B show a top cross-sectional view and a side view of an illustrative individual cell of the feature pattern of FIGS. 10A and 10B . Specifically, referring to FIG. 11A , each individual cell 1101 is characterized by a maximum width 1102 of width d, an individual side length 1103 of length d/2 and a wall thickness 1104 of thickness t. Referring to FIG. 11B , the height 1105 of cell 1101 is height h.
[0032] FIGS. 12A, 12B and 12 C show how an illustrative closed-cell feature pattern similar to the feature pattern of FIGS. 10A and 10B , here shown in cross-section, may be used illustratively to cause a droplet 1201 of liquid to reversibly penetrate the feature pattern. Specifically, each cell within feature pattern 1204 , such as cell 1101 having a hexagonal cross-section, is a completely closed cell once the droplet of liquid covers the opening of that cell. Thus, referring to FIG. 12A , each such closed cell over which the droplet is disposed contains a fluid having an initial temperature T=T 0 and an initial pressure P=P 0 . As used herein, the term fluid is intended to encompass both gases (such as, illustratively, air) and liquids that could be disposed within the cells of the feature pattern. The present inventors have recognized that, by changing the pressure within the individual cells, such as cell 1101 , the liquid droplet 1201 can be either drawn into the cells or, alternatively, repelled out of the cell. Specifically, referring to FIG. 12B , if the pressure within the cell 1101 is caused to be below the initial pressure (i.e., P<P 0 ), then the droplet above that cell will be drawn into the cell a distance related to the magnitude in reduction of the pressure P. Such a reduction in pressure may be achieved, illustratively, by reducing the temperature of the fluid within the cells such that T<T 0 . Such a temperature reduction may be achieved, illustratively, by reducing the temperature of the substrate 1205 and/or the feature pattern 1204 . One skilled in the art will recognize that any method of reducing the pressure within the cells, including any other method of reducing the temperature of the fluid within the cells, will have similar results. For example, each of the cells could be connected either in series or in parallel to one or more remote ballast gas reservoirs. The pressure of the gas in this reservoir could be changed, thus raising or lowering the pressure in the cells. Similarly, the pressure within the cells could be changed by moving a diaphragm disposed within each of the cells, thus displacing a fluid within the cell and varying the pressure within that cell. Additionally, as discussed more fully in the aforementioned copending patent applications, electrowetting may be used instead of pressure reduction to draw the liquid into the cells of the feature pattern 1204 . Specifically, by applying a voltage to the conducting drople 1201 , a voltage difference results between the liquid and the cells in the feature pattern 1204 . Hence, as discussed herein above, the droplet 1201 moves down and penetrates the nanostructure feature pattern 1204 until it comes into contact with the upper surface of substrate 1205 . Other methods of changing the pressure within the cells will be readily apparent to one skilled in the art in light of the teachings herein.
[0033] FIG. 12C shows how, by increasing the pressure to or above the initial pressure P 0 , it is possible to reverse the penetration of the droplet 1201 , whether that penetration was initiated by pressure reduction or by electrowetting. Once again, such a pressure increase may be achieved by changing the temperature of the fluid within the cells, illustratively in FIG. 8C to a temperature greater than the initial temperature T 0 . One illustrative method if increasing this temperature is to apply a voltage to electrodes 1002 in FIG. 10 in a way such they heat the insides of the cells. The increased temperature will increase the pressure within the cells above the initial pressure P 0 . The contact angle between the droplet and the elements of the feature pattern will thus change to θ 3 , which is smaller than θ 1 and the liquid will move out of the cells, thus returning droplet 1201 to a very low flow resistance contact with feature pattern 1204 . Once again, one skilled in the art will recognize that any method of increasing the pressure within the cells to reverse the penetration of the droplet 1201 , including any other method of increasing the temperature of the fluid within the cells, will have similar results.
[0034] The foregoing merely illustrates the principles of the invention. It will thus be appreciated that those skilled in the art will be able to devise various arrangements which, although not explicitly described or shown herein, embody the principles of the invention and are within its spirit and scope. For example, one skilled in the art, in light of the descriptions of the various embodiments herein, will recognize that the principles of the present invention may be utilized in widely disparate fields and applications. For example, while the embodiment disclosed herein is a battery having nanostructured surfaces, one skilled in the art will appreciate that such nanostructured surfaces may be used for other uses, such as in use as a thermostat. In such a case, the characteristics of the pattern of nanostructures and the liquid in contact with the nanostructures can be chosen in a way such that, upon a temperature increase of known amount, the liquid will penetrate the surface, thus achieving a desired result. One skilled in the art will be able to devise many similar uses of the underlying principles associated with the present invention, all of which are intended to be encompassed herein. All examples and conditional language recited herein are intended expressly to be only for pedagogical purposes to aid the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and conditions. Moreover, all statements herein reciting aspects and embodiments of the invention, as well as specific examples thereof, are intended to encompass functional equivalents thereof.
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A battery having a nanostructured battery electrode is disclosed wherein it is possible to reverse the contact of the electrolyte with the battery electrode and, thus, to return a battery to a reserve state after it has been used to generate current. In order to achieve this reversibility, the nanostructures on the battery electrode comprise a plurality of closed cells and the pressure within the enclosed cells is varied. In a first embodiment, the pressure is varied by varying the temperature of a fluid within the cells by, for example, applying a voltage to electrodes disposed within said cells. In a second illustrative embodiment, once the battery has been fully discharged, the battery is recharged and then the electrolyte fluid is expelled from the cells in a way such that it is no longer in contact with the battery electrode.
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BACKGROUND OF THE INVENTION
[0001] This invention relates to a spring pad for elastically supporting a felt cover. The felt cover is rolled on the periphery of a rotatable drum of a sheet ironing machine which is used to press and finish a flat sheet of material, such as a bed sheet, table cloth and so on.
[0002] The item to be ironed, using the sheet ironing machine, is finished by putting the item between a roller or drum and a bed which is heated by steam or a thermal medium of oil. The finishing procedure results in the drying, pressing and ironing, whilst the residual water contained in the washed item becomes vapour due to the heated bed. The vapour is discharged from the side of the roller.
[0003] On the periphery of the rotatable drum is rolled a spring pad, on the outer periphery of which is positioned a felt cover.
[0004] Conventionally, there is known a spring pad as disclosed in patent application EP0736627A1 by the same applicant as the present application. The said spring pad has a plurality of coil springs arranged in predetermined spaced relationship along the longitudinal extent of the upper side of a backing strip. The backing strip contacts the periphery of the roller of the sheet ironing machine. Said coil spring has a top plate at its centre transverse portion, Said top plate is made from a press machined stainless steel band. The said top plate is made by stamping an elongate strip material to leave adjacent plates connected to one another by frangible sections which are cut by pressing works.
[0005] With the conventional spring pad for a sheet ironing machine, however, the space between adjacent top plates becomes larger when the backing strip of the spring pad is rolled on the periphery of the roller, because the top plates are mounted slightly spaced from each other on each coil spring. The space between adjacent top plates causes a scar or unsightly wrinkle on the surface of the felt cover, which contacts each top plate. This causes poor ironing finishing, such as folds, wrinkles and so on.
[0006] To avoid such marks caused by the spacing of the top plates, a thicker felt cover is needed. The felt cover employs expensive heat resistant aramid fibre, and thus the thicker felt cover increases the manufacturing cost of the sheet ironing machine, as well as decreasing the ventilation effect. The decreased ventilation decreases a drying effect (in other words, increases drying time) and impacts the finished quality of the item being ironed.
SUMMARY OF THE INVENTION
[0007] The present invention seeks to provide a solution to the inconvenience of the conventional arrangement. As such, there is provided a spring pad for a sheet ironing machine of which adjacent top plates have no space between them, and which preferably overlap each other when a backing strip of the spring pad is rolled on the periphery of the roller. This results in no traces of wrinkles or marks on the item to be ironed. Additionally, the felt cover rolled on the top plates is thin. Furthermore, the spring pad enables a reduction in cost of the sheet ironing machine, thanks to the thin felt cover to be used as well as improved finishing quality and drying effect due to the increased ventilation.
[0008] Thus, according to a first aspect of the present invention, there is provided an elongate spring pad for a sheet ironing machine, the spring pad comprising: an elongate backing strip for rolling about a periphery of a roller of a sheet ironing machine; a plurality of coil springs positioned in spaced relationship along the longitudinal extent of the backing strip, each coil spring having a connecting portion at a first end by which the respective coil spring is engaged with the backing strip, a fixing portion at a second end opposite the first end and which extends transversely across the coil spring; a plurality of independent top plates, each top plate being provided on a second end of each coil spring opposite the first end; positioning means on each top plate by which each top plate is engaged with the respective coil spring; and one or more claws projecting outwardly from the top plate for releasably engaging a felt cover, each top plate contacting an adjacent top plate so that there are no spaces therebetween.
[0009] According to a second aspect of the invention, there is provided a flat sheet ironing machine comprising a bed having a part cylindrical recess, a roller mounted for rotation in the recess, a felt cover mounted on the roller, and an elongate spring pad in accordance with the first aspect of the invention between the roller and the felt cover, the backing strip of the spring pad being tightly wound about the drum, and the claws of the top plates releasably engaging the felt cover to hold the felt cover to the top plates.
[0010] To provide a solution to the problems mentioned above, the present invention provides a spring pad for a sheet ironing machine, which comprises a backing strip 2 for contact with a periphery of a drum or roller R of a sheet ironing machine P, a plurality of coil springs 3 arranged in specific regular spaced relationship on an upper side of the backing strip. The coil springs 3 have connecting portions 3 A via which the springs 3 are connected to the backing strip 2 at its lower surface, and fixing portions 3 B. Each fixing portion 3 B is at a top of the respective spring 3 , opposite the backing strip 2 , and extends centrally and transversely across the spring 3 . The spring pad also comprises a plurality of top plates 4 , each of which is connected via a positioning means 5 to the top of each coil spring 3 . The positioning means 5 is provided on a back side of each said top plate 4 and fixes each top plate 4 to the fixing portion 3 B at the top of each coil spring 3 . Each top plate 4 also includes claws 4 A on its upper side which, in use, softly catch the felt cover F. Each said top plate 4 overlaps an adjacent top plate 4 .
[0011] Said top plates 4 are arranged so that adjacent top plates 4 overlap each other, when the backing strip 2 of the spring pad is rolled on the periphery of roller R. Preferably, the direction of overlap is in the opposite direction to the direction of rotation of roller R. In other words, when the roller R is rotating in its normal operating condition, a leading edge of each top plate is received below a trailing edge of the next adjacent top plate. This prevents or reduces the possibility that one or more top plates are deformed and also that the top cover is removed from the claws as the roller R is rotating.
[0012] Positioning means 5 are formed as a pair of inwardly extending spaced guides or arms, at or adjacent to ventilation holes 4 B of top plate 4 .
[0013] Said ventilation hole 4 B of each top plate 4 is positioned opposite to, or to confront, ventilation hole 2 B formed in backing strip 2 . The back strip 2 has a plurality of the ventilation holes 2 B, formed in spaced relationship along the longitudinal extent of the backing strip 2 and at positions corresponding to each coil spring 3 .
[0014] The spring pad for a sheet ironing machine of the present invention, has said adjacent top pates 4 which are overlapped with each other so to provide an almost or substantially flat or smooth sur:face when the backing strip 2 is rolled on the periphery of roller R. Thus, no scars, marks or wrinkles are made on the surface of the thin felt F, which is rolled on the whole upper surfaces of the top plates 4 .
[0015] Water vapour, originating from retained water in a washed item and provided on thin felt F, passes through said ventilation holes 4 B of said top plates 4 and the ventilation holes 2 B of the back strip 2 , to the roller R.
[0016] The present invention provides for adjacent top plates 4 with no spaces between them, and which overlap each other when the backing strip 2 is rolled on the periphery of the roller, thus making no traces of wrinkles on the item to be ironed, even though the felt cover F, which is rolled on the top plates, is thin. Furthermore, the spring pad enables a reduction in the of the sheet ironing machine P, thanks to the thin felt cover to be used, as well as improving the finishing quality and drying effect due to the increased ventilation.
[0017] In the present invention, adjacent top plates 4 are overlapped with each other.
[0018] Due to the said adjacent top plates 4 being overlapped with each other, and this providing an almost or substantially flat or smooth surface when the backing strip 2 is rolled on the periphery of roller R, the surface of said felt cover F can be kept scar- or mark-free, even though said felt cover, which is rolled on all surfaces of the said top plate 4 , is thin.
[0019] Said positioning means 5 are formed backwardly at the ventilation hole 4 B of said top plate 4 to extend towards the coil spring. The positioning means are typically a pair of guides or arms provided in close spaced relationship, thus enabling easy attachment of said top plate 4 onto the coil spring 3 . The positioning means 5 also improve ventilation of the felt cover F, rolled on the top or upper surfaces of said top plates 4 .
[0020] Each ventilation hole 4 B of said top plate 4 is located opposite to or confronted with a respective ventilation hole 2 B of backing strip 2 . This improves the ventilation of the felt cover F, by providing an air flow path through the ventilation holes 4 B of the top plates 4 and ventilation holes 2 B of backing strip 2 . Thus in the finishing stage of the ironing process, the residual water in the ironed item becomes steam, which is be exhausted to the roller side through the ventilation holes 2 B of backing strip 2 .
[0021] The invention will now be more particularly described, by way of example only, with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIG. 1 is a plan view showing one embodiment of a spring pad, in accordance with the present invention;
[0023] FIG. 2 is a side view of the spring pad;
[0024] FIG. 3 is a plan view of a top plate of the spring pad;
[0025] FIG. 4 is a side view of the top plate of the spring pad;
[0026] FIG. 5 is a plan view of the coil springs and backing strip of the spring pad, showing connecting portions as dotted lines; and
[0027] FIG. 6 is a side view with enlarged portion showing the spring pad rolled on a periphery of a roller of a sheet ironing machine.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] Referring to the drawings, spring pad 1 , best seen in FIG. 6 , has a long belt shape and is spirally rolled from one end to another end of the roller R, along the peripheral surface thereof. Felt cover F is then rolled on the periphery of the spring pad 1 , and the spring pad 1 thus elastically supports the felt cover F.
[0029] The spring pad 1 is rolled on the roller R in such a manner that a first end of the spring pad 1 is fixed at the one side or end of the roller R, and then the spring pad 1 is rolled in a tight spiral along the peripheral surface of the roller R. The spring pad 1 is under tension, and its second end opposite the first end is connected to the other side or end of the roller R via a tension spring (not shown) which has hooks at both ends.
[0030] The sheet ironing machine shown in FIG. 6 comprises the roller R which is cylindrically formed to rotate around rotational axis S and which is arranged to contact a half-cylindrical bed Q or so called “chest”. Bed Q is supported by a stand, and heated by steam or a thermal medium of oil. The item to be ironed is inserted between said bed Q and said roller R and pressed, dried and finished by being pressed between said bed Q and roller R. Known urging means (not shown) urges the roller R towards the bed Q during pressing. The residual humidity or water contained in the item to be ironed becomes steam vapour, due to the heated bed Q and this vapour is exhausted through to the roller R.
[0031] A radius of the press surface of the heated bed Q coincides with or is complementarily matches a radius of roller R. The item to be ironed is taken or drawn between the press surfaces by the rotation of roller R. The item to be ironed is thus heated and pressed between heated bed Q and felt cover F. The ironed item is then discharged at the opposite side of the bed Q and roller R.
[0032] The spring pad 1 , as shown in FIGS. 1 and 2 , comprises a long belt-like backing strip 2 , typically made of stainless steel or zinc plated iron, which is rolled on the periphery of the roller R. So called ‘hybrid’, typically helically wound, coil springs 3 are located at specified spaced intervals on said backing strip 2 , and rectangular shaped top plates 4 , typically made of stainless steel for example, are fixed at the upper end of each of said coil springs 3 , opposite the backing strip 2 . Each coil spring 3 stands an equal specified height from said backing strip 2 . A fixing portion 3 B is provided at the upper end of each coil spring 3 . The fixing portion 3 B extends horizontally and transversely across the coil spring 3 . Each coil spring 3 is integrally formed with or connected to each adjacent coil spring 3 via wire connecting part 3 A, and the interconnected coil springs 3 are continuously connected to the backing strip 2 via the connecting portion 3 A being wound around a back side or lower side of the backing strip 2 , as best understood from FIGS. 2 and 5 .
[0033] Said backing strip 2 , as shown in FIG. 5 , has projected portions 2 A which are formed at equal intervals along both side edges of the backing strip 2 , and so as to face each other across the backing strip 2 . The connecting portion 3 A, which is in the form of wire between adjacent coils 3 , is hooked on or wound around each said projected portion 2 A. Each ventilation hole 2 B is formed between two adjacent projected portions 2 A of said backing strip 2 .
[0034] The top plate 4 is typically formed by press-machining and bending a stainless steel plate. As shown in FIGS. 3 and 4 , a pair of claws 4 A, which slant upwardly in a direction opposite the coil spring 3 by more than 45 degrees are formed symmetrically on the upper surface of top plate 4 , so that they can flexibly hooks the felt cover F.
[0035] The symmetrically formed U-shaped holes on said top plate 4 are typically formed by press machining. A portion of the top plate 4 , which is pressed downwardly or inwardly to form the U-shaped holes, forms a pair of guides or arms of positioning means 5 . A pair of left and right U shaped holes, making four holes in total opposite or confronting a respective ventilation hole 2 B of the backing strip 2 , are formed in said top plate 4 .
[0036] The transverse fixing portion 3 B of coil spring 3 is positioned between the guides or arms of positioning means 5 . The fixing portion 3 B is fixed to the positioning means 5 by crimping, welding or any other suitable means. The adjacent top plates 4 , as shown in FIGS. 1 and 2 , are dimensioned to overlap each other when the backing strip 2 is extended straight or rectilinear.
[0037] As shown in FIG. 6 , when the backing strip 2 is rolled on roller R, and is thus arcuate or curved like a circle, the adjacent top plates remain overlapped, but to a lesser extent.
[0038] The adjacent top plates 4 are slightly overlapped when the backing strip 2 is rolled on the roller R, and thus produce a curved formation. In this case, the overlapped adjacent top plates 4 form a slight step, but have no space between them, Consequently, adjacent top plates 4 are always in contact with each other, irrespective of the shape of the longitudinal extent of the spring pad 1 .
[0039] Preferably, the direction of overlap of the top plates 4 is in the opposite direction to the direction of rotation of roller R. In other words, when the roller R is rotating in its normal operating condition, a leading edge of each top plate is received below a trailing edge of the next adjacent top plate. This prevents or reduces the possibility that one or more top plates are deformed, and also that the top felt cover F is removed from the claws as the roller R is rotating.
[0040] Art example of usage, assembly and movement of the spring pad 1 is now explained. First of all, when the spring pad 1 is manufactured, as shown in FIGS. 1, 2 and 5 , the coil springs 3 are positioned with the same space between them along the longitudinal extent of the backing strip 2 . The connecting portion 3 A is hooked over and wound around the backing strip 2 , between the projected portions 2 A.
[0041] The top plates 4 are arranged and fixed at the top or upper ends of the coil springs 3 , so that adjacent said top plates 4 overlap each other when the baking strip 2 is extended in a straight line. The transverse fixing portion 3 B at the top of each coil spring 3 is placed between a pair of the guides, being the positioning means 5 , which is then pinched or welded to fasten the top plate 4 to the coil spring 3 .
[0042] To roll the spring pad 1 on the periphery of roller R of sheet ironing machine P, the starting or first end of the backing strip 2 is fixed at the one side or end of the roller R and the spring pad 1 is tightly spirally rolled under tension around the periphery of the roller R. A rolling device (not shown) is used, which engages the ventilation holes 2 B of the backing strip 2 to wind the spring pad 1 onto the roller R. The opposite end of spring pad 1 is hooked on one end of a tension spring (not shown) which has hooks at both ends, and the other hooked end of the tension spring is hooked onto the side or end of the roller R to retain the spring pad 1 securely on the periphery of the roller R.
[0043] In this condition and with the backing strip 2 rolled around the periphery of roller R, as shown in FIG. 6 , the tops or ends of the coil springs 3 opposite the backing strip 2 become further spaced apart. It is possible for the top plates 4 to become un-overlapped, whereby adjacent edges of adjacent top plates lie in the same plane. However, in this case, the adjacent top plates 4 still contact each other, even though there is no step therebetween, due to there being no overlap. Consequently, there is still no space between the top plates 4 .
[0044] If the overlapped portions of the top plates 4 remained when the backing strip 2 is rolled on the periphery of roller R, the adjacent top plates 4 form steps, but there is no space between the top plates 4 .
[0045] Thin felt cover F is rolled on the spring pad 1 . The claws 4 A of the upper surface of the top plate 4 catch the inside or lower surface of the felt cover F. The entire lower surface of the felt cover F thus contacts the whole upper surface of the top plates 4 . Thus, no marks are made on the surface of felt cover F, because the felt cover F is elastically supported by the spring pad 1 and because there is no space between the adjacent top plates 4 .
[0046] When the sheet ironing machine P is used, the heated surface of bed Q is heated by the heat source and the roller R is rotated to stick or draw the item to be ironed between the pressing surfaces of the bed Q and the roller R. The item is thus pressed on to the heated bed Q, before being discharged at the opposite side of the roller R.
[0047] The humidity or residual water retained in the item to be ironed becomes steam, due to the heated bed Q, and the resulting vapour is thus discharged from the centre of the roller 1 via the flow path formed by the ventilation holes 4 B in the top plates 4 , the interiors of the coil springs 3 , and the ventilation holes 213 in the backing strip 2 .
[0048] Thus the item to be ironed has no trace of wrinkles or marks, due to the felt cover remaining entirely smooth.
[0049] The embodiments described above are given by way of examples only, and various other modifications will be apparent to persons skilled in the art without departing from the scope of the invention, as defined by the appended claims.
EXPLANATION OF MARKS
[0050] P: Sheet ironing machine
[0051] Q: Bed
[0052] R: Roll
[0053] F: Felt cover
[0054] S: Rotating axis
[0055] 1 : Spring pad
[0056] 2 : Backing strip
[0057] 2 A: Projected portion
[0058] 2 B: Ventilation hole
[0059] 3 : Coil spring
[0060] 3 A: Connecting portion
[0061] 3 B: Transverse fixing portion
[0062] 4 : Top plate
[0063] 4 A: Claw
[0064] 4 B: Ventilation hole
[0065] 5 : Positioning measures
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An elongate spring pad for a sheet ironing machine, comprises an elongate backing strip for rolling about a periphery of a roller of a sheet ironing machine; a plurality of coil springs positioned in spaced relationship along the longitudinal extent of the backing strip, each coil spring having a connecting portion at a first end by which the respective coil spring is engaged with the backing strip, and a fixing portion at a second end opposite the first end and which extends transversely across the coil spring; a plurality of independent top plates, each top plate being provided on a second end of each coil spring opposite the first end; positioning means on each top plate by which each top plate is engaged with the respective coil spring; and one or more claws projecting outwardly from the top plate for releasably engaging a felt cover, each top plate contacting an adjacent top plate so that there are no spaces therebetween.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a sensor device for detecting at least one flow property of a fluid medium, e.g., in the intake tract or the charge tract of an internal combustion engine.
2. Description of the Related Art
Flow meters are used to ascertain the air flow in the intake tract or the charge tract of an internal combustion engine. Since the weight ratios are important in the chemical process of combustion, the mass flow rate of the intake/charge air is to be measured, for which volume measuring methods or impact pressure measuring methods are used to some extent.
Various types of sensors are known for measuring the air mass throughput. One such type of sensor is the so-called hot-film mass airflow sensor, such as that described in one possible specific embodiment in published German patent application document DE 103 45 584 A1. The flow meter according to published German patent application document DE 103 45 584 A1 has a sensor housing having a cavity for accommodating an electronic module, which is separated from a bypass measuring channel. The electronic module here has a carrier profile, which is formed essentially on a bottom plate having side webs molded on the opposing longitudinal sides. The electronic module also has a plastic carrier tongue, which is situated on one of the head sides of the carrier profile and, as a carrier, accommodates the sensor element. A circuit board equipped with electronic components and printed conductors is usually attached to the bottom plate of the carrier profile to provide an evaluating electronic unit.
Published German patent application document DE 103 45 584 A1 also describes how the electronic module is held by the side webs in the cavity provided here after being inserted into the sensor housing, while achieving a clamping effect. The carrier here protrudes into the bypass measuring channel through an outlet opening between the latter and this cavity.
In addition, published German patent application document DE 44 26 102 A1 describes a sensor carrier for a device for measuring the mass of a flowing medium, which is characterized in that the sensor carrier has a frame element and a holding element, the frame element having an opening which is covered by the holding element situated at the rear, thereby forming the recess for the sensor element.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a sensor device for detecting at least one flow property of a fluid medium, in particular for detecting the air flow rate in the intake tract or the charge air tract of an internal combustion engine. The sensor device has at least one sensor housing, which may be introduced into the fluid medium and has at least one housing body and at least one cover. In addition, the sensor housing preferably has at least one channel through which the fluid medium may flow. In addition, the sensor device has a sensor element for detecting the flow property of the fluid medium, which is preferably mounted on a top side of a carrier, the carrier having a bottom side opposite the top side. The carrier is preferably situated at least partially in the channel. The channel may also be a side channel or a bypass channel branching off from a main flow channel or a main channel.
With the sensor device according to the present invention, it is also provided that, at the location of the sensor element in a sectional plane parallel to a main flow direction of the fluid medium in the channel, the carrier has a cross section which becomes wider in at least some sections parallel to the main flow direction of the fluid medium. In other words, the thickness of the carrier increases along the main flow direction and decreases, preferably steadily, opposite the main flow direction accordingly. Furthermore, it is important in particular that the cross section becomes wider in the main flow direction, at least up to the rear of the sensor element.
With the resulting tapering or constriction of the measuring channel, preferably steadily, in particular upstream from and in the area of the sensor element, it has advantageously been found that it is possible in this way to have an effective influence on the oncoming flow of the fluid medium against the sensor element and thereby substantially improve the stability, in particular the reproducibility, of the measurements, the comparability and signal-to-noise ratio. In this context, it is desirable in particular that an equally steady increase in the velocity of the fluid medium is achieved due to this steady tapering of the measuring channel, thus also improving the advantages mentioned above.
In addition, the dependence of the comparability of the positioning of the housing body, of the cover and of the carrier in relation to one another is reduced in an advantageous manner, which permits a higher precision of the sensor devices compared and decreases rejects due to the production technology accordingly in an advantageous manner with the same manufacturing tolerances. As has also been found here, the influence of the position of the cover and the housing body is reduced significantly because the sensor element in particular is positioned on the carrier and the carrier contributes significantly toward the tapering of the channel. It is conceivable here in particular that complete independence of the position of the cover and the housing body is achieved when tapering of the channel is implemented completely by the carrier. Due to the widening of the cross section of the carrier according to the present invention and the associated tapering of the channel, in particular a reduction in the cross section of the channel, the flow velocity and the pressure of the fluid medium are influenced in the area of the sensor element and therefore an increase in accuracy is possible in an advantageous manner.
It may also be advantageous if the carrier is designed to be wedge-shaped in at least some sections at the location of the sensor element. A corresponding wedge shape of the carrier thus also has advantageous effects in the manner described above by a widening of the cross section of the carrier and a corresponding tapering of the cross section of the channel.
According to the idea on which the present invention is based, it may also be provided that the carrier has an inflow edge, in particular a contoured inflow edge. In other words, the inflow edge preferably has a fluidically optimized contour, the inflow edge having a contour having a shape starting from a tip or an apex point—as viewed in the main flow direction of the fluid medium—such that the cross section of the carrier also widens increasingly in the main flow direction of the fluid medium in the area of the inflow edge starting from the tip of the carrier.
According to another specific embodiment of the present invention, it may be provided that the carrier of the sensor device has an apex angle γ, as viewed in the main flow direction. This apex angle is defined in particular by the two straight lines spanning the apex angle, these lines being obtained by drawing two lines in tangent to both the top side and the bottom side of the carrier. These two straight lines usually intersect in front of the carrier, as viewed in the main flow direction. “Drawing a tangent” is understood here in particular to mean that the straight line does not pass through the cross-sectional area of the carrier but instead merely contacts the carrier, under formation of one or multiple contact points.
In addition, it may advantageously be provided that the carrier of the sensor device has a recess on the top side, the sensor element being introduced into the recess in such a way that the measuring surface of the sensor element has fluid medium flowing over it. It may also advantageously be provided that the sensor element completely fills up the recess and the measuring surface is flush with the top side of the carrier.
The measuring surface may be equipped, for example, with at least one heating element and at least two temperature sensors, the sensor device optionally being equipped, for example, to detect, with the aid of the temperature sensors, an influence on a temperature distribution due to the flow of the fluid medium. For this purpose, one temperature sensor is preferably situated, viewed in the flow direction of the fluid medium, upstream and one temperature sensor is situated downstream from the heating element.
According to another embodiment of the proposed sensor device, it may be provided that at least the bottom side and/or the top side of the carrier has/have a planar shape in at least some sections.
Alternatively or additionally, it may also be provided that at least the bottom side and/or the top side of the carrier has/have a shape which is concave and/or convex, in particular being curved in at least some sections.
This advantageously creates the possibility of having an advantageous influence on the flow of the fluid medium through a corresponding design of a surface contour on the bottom side and/or the top side of the carrier.
In addition, with the proposed sensor device, it may also be provided that at least on the bottom side and/or the top side of the carrier two or more regions of a different shape abut in pairs, forming a transitional edge.
The design of the carrier is not limited to symmetrical or conical geometries in particular. Consequently, a variety of possible designs of the shape of the bottom side and/or the top side of the carrier are conceivable. With another embodiment of the sensor device in particular, it may be provided that the top side and the bottom side have a shape, which is described in greater detail in the following itemization. In particular, it may be provided here that the top side and the bottom side have a planar shape in at least some sections and the top side runs at a first pitch, preferably >0°, in particular >10°, to the main flow direction, and the bottom side runs at a second pitch, preferably >0°, in particular >10°, to the main flow direction. Furthermore, the first pitch and the second pitch are equal. In general, the pitch refers to the angle which is enclosed or spanned in a sectional plane by a vector of the main flow direction in the area of the carrier and a vector tangentially along the shape of either the top side or the bottom side of the carrier or a wall section of the housing body or of the cover.
Alternatively, the shape of the top side and the bottom side may be designed in such a way that the top side and the bottom side each have a planar shape in at least some sections, the top side running at a first pitch, preferably >0°, in particular >10°, to the main flow direction, and the bottom side running at a second pitch, preferably >0°, in particular >10°, to the main flow direction, the first pitch and the second pitch being different.
According to another alternative embodiment, it may be provided for the top side and the bottom side to each have a planar shape in at least some sections, the top side running in parallel to the main flow direction, and the bottom side running at a second pitch, preferably >0°, in particular >10°, to the main flow direction.
Conversely, it may likewise be provided that the top side and the bottom side each have a planar shape in at least some sections, the top side running at a first pitch, preferably >0°, in particular >10°, to the main flow direction, and the bottom side running in parallel to the main flow direction.
It is likewise conceivable that the top side has a shape with a concave curvature in at least some sections. A concave shape is understood in particular to mean that the curvature bulges centrally toward a straight sectional line running essentially in parallel to the main flow direction through the carrier. In other words, the cross-sectional area of the carrier is reduced by the concave curvature, whereas it would increase due to a convex curvature having the same edge points of the curvature.
It may likewise correspondingly be provided that the bottom side has a concave curvature in at least some sections.
In addition, it is possible to design the shape of the carrier in such a way that the bottom side has a first section having a first shape in the main flow direction and a second section having a second shape connected to the first section in the main flow direction, a transitional edge being situated essentially across the main flow direction between the first section and the second section.
The proposed sensor device may also be designed in such a way that the carrier tapers on its downstream end, i.e., at its rear end in the main flow direction, in particular so that the shape of the top side and the shape of the bottom side meet and merge at an apex.
According to another embodiment of the sensor device, it may also be provided that the housing body and/or the cover has/have a geometry in which the housing body and/or the cover is/are designed to cause the channel to taper in the area of the carrier. This yields in particular the advantage that the influence of the carrier on the flow of the fluid medium is advantageously supported by the geometry of the housing body and/or that of the cover.
In addition, it may also be provided that the cross-sectional shape of the carrier is adapted essentially to the geometry of the housing body and/or that of the cover. This means in particular that the shape of the top side of the carrier cooperates with the geometry of the cover in such a way that the flow of the fluid medium between the carrier and the cover may be influenced in a targeted manner. Furthermore, the bottom side of the carrier here also has a shape which cooperates with the geometry of the housing body in particular and seeks to influence the flow of the fluid medium between the bottom side of the carrier and the housing body, optionally in the same way as the flow of the fluid medium between the top side of the carrier and the cover, or to induce a different flow through a different influence.
In general, it may also be provided that the sensor device, in particular the sensor housing of the sensor device, is designed at least partially as a plug sensor, and the plug sensor is introducible into a flow tube of the fluid medium.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a schematic diagram of the sensor housing of a sensor device according to the present invention without a cover placed on the housing body.
FIG. 2 shows a sectional diagram of a possible specific embodiment along line A-A′ in FIG. 1 .
FIG. 3 shows a sectional diagram of another specific embodiment along line A-A′ in FIG. 1 .
FIGS. 4 a through 4 f illustrate various diagrams of possible embodiments of the carrier.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows a schematic diagram of one possible specific embodiment of sensor device 10 according to the present invention, which shows in particular a sensor housing 12 having an open housing body 14 , in other words, without a cover 16 , which is provided for closing housing body 14 .
The diagram in FIG. 1 also indicates that a channel 18 , which has an inflow opening 20 and an outflow opening 22 , is situated in housing body 14 . Inflow opening 20 is preferably situated on an end face of housing body 14 directed opposite main flow direction 24 , outflow opening 22 preferably at the same time being situated at a right angle to inflow opening 20 within a chamber carrying the fluid medium. In addition, the preferred specific embodiment of sensor device 10 according to the present invention has another outlet opening 26 , which is formed following inflow opening 20 , as viewed along main flow direction 24 . This permits a preferred embodiment of channel 18 as a bypass channel.
As also shown in FIG. 1 , sensor device 10 has a carrier 28 situated in channel 18 in at least some sections, a sensor element 30 being held on this carrier inside channel 18 . It may thus be ensured that a substream of the fluid medium flows along main flow direction 24 through inflow opening 20 following the course of channel 18 to outflow opening 22 and flows over carrier 28 and sensor element 30 .
FIG. 2 shows a sectional diagram of one possible specific embodiment along line A-A′ as shown in FIG. 1 .
The diagram in FIG. 2 shows in particular that housing body 14 has a pitch α which reduces the cross section of channel 18 in front of and in the area of carrier 28 . In addition, cover 16 has a pitch β which may be designed to be different from pitch α of housing body 14 , for example, as shown here, and influences the cross section of channel 18 only in an area in front of carrier 28 . Geometry 32 of housing body 14 is described by the wall section of housing body 14 with pitch α as well as the wall section in channel 18 adjacent thereto and aligned in parallel to main flow direction 24 . A corresponding geometry 34 of cover 16 is described by the wall section of cover 16 , which runs at pitch β in some sections, and the section of cover 16 runs adjacent thereto downstream and essentially in parallel to main flow direction 24 .
FIG. 2 also shows that in the specific embodiment of sensor device 10 shown here, sensor element 30 is situated in a recess 36 , preferably on top side 38 of carrier 28 . Carrier 28 also has a bottom side 40 situated opposite top side 38 . The shape of top side 38 and bottom side 40 of carrier 28 shown here form in particular an inflow edge 42 directed opposite main flow direction 24 . When viewed in main flow direction 24 , the shape of top side 38 and of bottom side 40 of carrier 28 thus contributes to the tapering of channel 18 in accordance with the idea according to the present invention. Carrier 28 here has a apex angle γ, which corresponds to the angle between a straight line applied to top side 38 and to bottom side 40 .
Thus, in general, the pressure and/or the flow velocity of the fluid medium may be influenced indirectly by the tapering of channel 18 , in particular a reduction in the cross section of channel 18 in the area of carrier 28 . As shown in FIG. 2 , the flow velocity along top side 38 of carrier 28 may differ from the flow velocity on bottom side 40 of carrier 28 , in particular due to the difference in design of geometry 32 of housing body 14 and geometry 34 of cover 16 .
FIG. 3 shows a sectional diagram of another specific embodiment of sensor device 10 along line A-A′ in FIG. 1 . Sensor device 10 illustrated in FIG. 3 differs from sensor device 10 illustrated in FIG. 2 only in geometry 32 of housing body 14 , geometry 34 of cover 16 , the design of carrier 28 and the resulting different design of channel 18 .
As may be derived in detail from the diagram in FIG. 3 , geometry 32 of housing body 14 is formed by a wall section, which is merely planar. At the same time, geometry 34 of cover 16 is formed by a wall section in parallel to main flow direction 24 . According to this specific embodiment of sensor housing 12 of sensor device 10 , no tapering of channel 18 is achieved by geometry 32 of housing body 14 and geometry 34 of cover 16 , when considered alone. The tapering of channel 18 , in particular a reduction in the channel cross section, is created exclusively by carrier 28 according to the specific embodiment shown in FIG. 3 . Carrier 28 also reveals that apex angle γ is obtained from two partial angles δ, γ, partial angle δ corresponding to the pitch of top side 38 of carrier 28 in relation to main flow direction 24 . Accordingly, partial angle ε is formed by the pitch of bottom side 40 of carrier 28 in relation to main flow direction 24 .
In addition, the diagram in FIG. 3 indicates that top side 38 of carrier 28 is formed by an area 44 having a planar shape and by an additional area adjacent to area 44 downstream and having a different angle of inclination. Accordingly, a transitional edge 46 is formed on top side 38 of carrier 28 in the transition of the two areas into one another. According to the specific embodiment of sensor device 10 shown in FIG. 3 , it may also be provided that top side 38 and bottom side 40 of carrier 28 contact one another in a shared vertex on a side of carrier 28 opposite inflow edge 42 in main flow direction 24 . However, it is not absolutely necessary for this vertex to lie on a plane of inflow edge 42 , as viewed in main flow direction 24 . This may optionally be situated in particular on a side facing top side 38 or bottom side 40 in relation to inflow edge 42 in main flow direction 24 due to an asymmetrical design of top side 38 and bottom side 40 of carrier 28 .
In the following individual diagrams a) through f) of FIG. 4 , various possible embodiments of carrier 28 are shown, in particular the shape of top side 38 or of bottom side 40 . The individual diagrams of different embodiments of carrier 28 are described below essentially on the basis of their differences in comparison with one another, in particular the differences in comparison with the preceding diagram.
FIG. 4 a thus shows a carrier 28 having an area 44 of a planar shape provided on top side 38 as well as on bottom side 40 of carrier 28 .
FIG. 4 b shows a carrier 28 , which also has an area 44 having a planar shape on top side 38 as well as on bottom side 40 of carrier 28 , but top side 38 of carrier 28 runs essentially in parallel to main flow direction 24 (not shown), whereas bottom side 40 of carrier 28 is set at an angle in relation to main flow direction 24 .
However, the diagram in FIG. 4 c shows a carrier 28 , whose bottom side 40 runs essentially in parallel to main flow direction 24 (not shown), so that top side 38 of carrier 28 has a pitch in relation to main flow direction 24 .
Carrier 28 according to the diagram in FIG. 4 d has an area 48 having a concave shape on top side 38 as well as on bottom side 40 .
However, the diagram in FIG. 4 e shows that carrier 28 illustrated here has an area 44 on top side 38 having a planar shape, which runs obliquely to main flow direction 24 . Bottom side 40 of carrier 28 illustrated here also has an inclined area 44 having a planar shape, when viewed in main flow direction 24 , to which an additional area 44 also having a planar shape but in parallel to main flow direction 24 is connected, forming a transitional edge 46 . However, the diagram in FIG. 4 f indicates that top side 38 of carrier 28 shown here is formed from an area 48 having a concave shape, whereas bottom side 40 initially also has an area 48 having a concave shape in main flow direction 24 , an additional area 50 having a convex shape connected to same, forming a transitional edge 46 .
The possible embodiments of carrier 28 are not exhausted in the diagrams of FIGS. 2 through 4 but instead may be formed by any combination of different features of top side 38 or bottom side 40 of carrier 28 in planar, convex or concave sections in arbitrary apex angles γ, in particular pitches δ, ε.
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A sensor device for detecting a flow property of fluid medium, e.g., an air flow in the intake tract or the charge air tract of an internal combustion engine, includes: a sensor housing introduced into the air flow and having at least one housing body, at least one cover, and at least one channel through which the fluid medium flows; a sensor element for detecting the flow property, the sensor element being held on a top side of a carrier. The carrier is situated at least partially in the channel and has a cross section which becomes wider in parallel with the main flow direction of the fluid medium at the location of the sensor element in a sectional plane in parallel to the main flow direction of the fluid medium in the channel.
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CROSS-REFERENCE TO RELATED APPLICATION
This application is a divisional application of the commonly assigned, copending U.S. application Ser. No. 07/251,817, filed Oct. 3, 1988, entitled "A METHOD OF AND APPARATUS FOR CONTINUOUSLY CRIMPING THERMOPLASTIC FILAMENTS", now U.S. Pat. No. 4,877,570, granted Oct. 31, 1989.
BACKGROUND OF THE INVENTION
The present invention relates to a new and improved method of, and apparatus for, continuously texturing or crimping thermoplastic filaments.
In its more particular aspects, the texturing or texturizing method of the present invention is of the type wherein thermoplastic filaments are blown-in or introduced in the form of a filament bundle by means of a jet or stream of a heated medium with the aid of a jet nozzle into a stuffing chamber of elongate curvature or curved configuration substantially tangentially with respect to such elongate curvature of the stuffing chamber and at a forwarding speed which is greater than the circumferential velocity of the stuffing chamber.
As to the texturing or texturizing apparatus of the present development such is of the type which comprises a jet nozzle for introducing or blowing-in a filament bundle by means of a jet or stream of a medium, such as air, steam or mixtures thereof, into an annular or ring-shaped rotatable and drivable stuffing chamber. This stuffing chamber possesses an inlet or blow-in or receiving zone or region for receiving and crimping the filament bundle, a treatment or heat transfer zone or region for heating or cooling the received filaments of the filament bundle and a delivery zone or region for delivering or outfeeding the crimped filaments to a subsequent conveying element or fiber bundle-lifting or take-off element or means, for example, a cooling drum or drafting roller or conveying roller.
The main criteria as concerns crimping thermoplastic filaments, also sometimes referred to in the art as filament threads or yarns, are intense filament crimping in the crimping technique apparatus and durability of the filament crimping following the crimping operation. As to such type of filament crimping technique such constitutes a stuffing crimping operation wherein a filament bundle, which has been heated by a heated gaseous medium, is blown into a stuffing chamber where the stuffed filament bundle is brought into a crimped condition within the stuffing chamber because of the decelerated speed of conveyance of the filament bundle within the stuffing chamber. In this crimped condition the filament cools below the softening point so that when the crimped filament bundle is again withdrawn there remains a permanent crimp.
Such type of method is known, for example, from German Published Patent Application No. 2,110,670, published Jan. 27, 1972. Here a jet nozzle blows-in or introduces the filament substantially tangentially into an elongate curved tunnel-like stuffing chamber. This stuffing chamber is provided in the circumferential or peripheral direction with a cooling drum which has a perforated surface. Cooling air is ejected through such perforated surface so that, as previously mentioned, the stuffed filament is cooled to produce thereat a permanent crimp.
This problem of fabricating a crimped filament is solved in a somewhat different manner in the apparatus which has been disclosed in German Published Patent Application No. 2,507,752, published Aug. 26, 1976. Here the filament thread which has been heated and pre-drafted by heated godets and after issuing from a jet nozzle is hurled against a screen wall in order to experience pre-crimping. The filament thread rebounding from the screen wall is then engaged by needles of a rotating belt so that the pre-crimped filament thread forms a plug between the needles. These needles then convey the plug into a heating channel or passage which narrows in order to compress the plug. Following the heating channel or passage the plug is then again released by means of a release device.
U.S. Pat. No. 3,816,887, granted June 18, 1974 discloses another construction of bulking or crimping apparatus wherein the filaments are blown-in or introduced in the form of a filament bundle or bunch by means of a stream of a heated medium and with the assistance of a jet nozzle into an elongate curved stuffing chamber substantially tangentially with respect to the curvature thereof and at a velocity greater than the circumferential velocity of the stuffing chamber. The injected filament bundle thus has imparted thereto a crimp which is subsequently cooled at the peripheral region of the stuffing chamber. The stuffing chamber comprises a groove formed in a cooling drum, and this groove is covered near to the site of blowing-in the filaments so that there is formed a closed chamber. Also, the base or floor of the groove is perforated so that external air can be sucked-in to cool the filaments. The crimped filaments are delivered at a predetermined location of the periphery of the groove to a subsequently arranged conveyor element.
One important aim or objective of a method or apparatus for continuously crimping thermoplastic yarns or threads is that the complete operation must not only give a result which is satisfactory from the technical point of view but it must also be very economical--i.e., operating conditions must be satisfactory and performance must be high. Operating conditions improve as less auxiliary agents, such as air, are required for cooling, or also improve in relation to the simplicity of construction of the crimping apparatus in order to achieve the same technological result with high efficiency, the term "technological result" denoting crimp density and the durability or retentiveness of the crimp in the filament bundle during subsequent process steps.
A disadvantage of the heretofore discussed prior art is that most of the components or parts bounding the actual stuffing chamber are stationary and therefore very dependent on friction or frictional effects.
SUMMARY OF THE INVENTION
Therefore, with the foregoing in mind it is a primary object of the present invention to provide a new and improved method of, and apparatus for, texturing filament yarns or threads in a manner which is not associated with shortcomings or drawbacks existing in the prior art.
Another important object of the present invention is direct to the provision of a new and improved method of, and apparatus for, crimping filament yarns or threads in a very simple manner and using few auxiliary means at a filament yarn or thread velocity of from at least 3,000 to 5,000 m/min.
Yet a further significant object of the present invention is directed to a new and improved method of, and apparatus for, texturizing filament yarns or threads with a jet nozzle and stuffing chamber coacting and structured such that the treatment medium necessary for texturing can issue at all sides from the filament bundle located in the stuffing chamber.
A further notable object of the present invention is directed to the provision of an improved method of, and apparatus for, texturing or crimping filament yarns or threads in a highly efficient and reliable fashion at relatively high throughput velocities and under favorable treatment conditions affording efficacious efflux of a treatment medium which has been brought into crimp-imparting relationship with the filament yarn or thread to be textured or crimped.
Now in order to implement these and still further objects of the present invention, which will become more readily apparent as the description proceeds, the texturing or crimping method of the present development, among other things, is manifested by the features that the stuffing chamber is constructed such that the medium required for the crimping of the filament bundle can escape or efflux at all sides from the filament bundle located in the stuffing chamber. In particular, the texturing or crimping method of the invention contemplates positively retaining or holding the infed filament bundle such that it is free at all sides for the essentially unimpeded outflow or efflux of the medium employed for the texturing or crimping of the filament bundle. Retention of the infed filament bundle is accomplished such that the filament bundle is positively held out of contact with the base or floor of the stuffing chamber and in a suspended state within the stuffing chamber. The infed filament bundle is preferably retained out of contact with the base of the stuffing chamber by holding such at the region of the upper half of the height of fluid or air pervious walls of the stuffing chamber.
As indicated heretofore the invention is not only concerned with the aforementioned method of texturing or crimping filament yarns or threads or filament bundles or the like, but also is concerned with apparatus constructions for the performance of the method aspects. The texturing or crimping apparatus of the present development, among other things, is manifested by the features that the stuffing chamber comprises two air-pervious annular or ring-shaped walls disposed in spaced-apart relationship with respect to one another on a texturing wheel. The jet nozzle substantially tangentially opens or enters between the mutually spaced walls with respect to the circumferential or peripheral surface of the texturing wheel and which forms the base or floor of the stuffing chamber and at a distance from such floor or base of the stuffing chamber such that the filament bundle is retained or held between these two mutually spaced walls in a manner that it neither lies or bears upon such base or floor nor at the outer edges or end regions of the walls.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein throughout the various figures of the drawings, there have been generally used the same reference characters to denote the same or analogous components and wherein:
FIG. 1 schematically illustrates in front view an exemplary embodiment of texturing or crimping apparatus constructed according to the invention;
FIG. 2 schematically illustrates in front view a modified exemplary embodiment of texturing or crimping apparatus constructed according to the present invention;
FIG. 3 schematically illustrates in front view a further modified exemplary embodiment of texturing or crimping apparatus constructed according to the present invention;
FIG. 4 is a fragmentary partial sectional view depicting details of the texturing or crimping apparatus of the arrangement of FIGS. 1 to 3;
FIG. 4a is a fragmentary cross-sectional view of the arrangement of FIG. 4, taken substantially along the section line 1--1 thereof;
FIG. 4b is a sectional view, like the showing of FIG. 4a, depicting a modification of the arrangement of FIG. 4;
FIG. 5 is a fragmentary view of a modification of the arrangement of FIG. 4;
FIG. 5a is a cross-sectional view of the arrangement of FIG. 5, taken substantially along the line 2--2 thereof;
FIG. 6 is a fragmentary view of a further modification of the arrangement of FIG. 4;
FIG. 6a is a cross-sectional view of the arrangement of FIG. 6, taken substantially along the line 3--3 thereof;
FIG. 7 is a fragmentary view of a still further modification of the arrangement of FIG. 4;
FIG. 7a is a cross-sectional view of the arrangement of FIG. 7, taken substantially along the line 4--4 thereof;
FIG. 8 is a fragmentary view, partially in section of a detail of the arrangement of FIG. 5, taken substantially along the line 5--5 thereof;
FIG. 9 is a fragmentary view, partially in section of a further modified detail of the arrangement of FIG. 5, taken substantially along the line 5--5 thereof;
FIG. 10 is a fragmentary view, partially in section of a still further modified detail of the arrangement of FIG. 5, taken substantially along the line 5--5 thereof;
FIG. 11 illustrates in fragmentary view a variant construction of the arrangement of FIG. 5 and depicted on a somewhat enlarged scale;
FIG. 12 illustrates a variant construction of the detail of FIG. 5 in fragmentary view and somewhat on an enlarged scale, as seen when looking in the direction of the arrow 6 of FIG. 5;
FIG. 13 illustrates a further variant construction of the detail of FIG. 5 in fragmentary view and somewhat on an enlarged scale, again as seen when looking in the direction of the arrow 6 of FIG. 5;
FIG. 14 illustrates a still further variant construction of the detail of FIG. 5 in fragmentary view and somewhat on an enlarged scale, likewise as seen when looking in the direction of the arrow 6 of FIG. 5;
FIG. 15 illustrates in fragmentary view a modification of the texturing or crimping apparatus of the present development, particularly as concerns the taking-off or lifting means for the removal of the treated filament bundle from the texturing wheel;
FIG. 16 illustrates in fragmentary view a further modification of the texturing or crimping apparatus of the present development, particularly as again concerns the taking-off or lifting means for the removal of the treated filament bundle from the texturing wheel;
FIG. 17 likewise illustrates in fragmentary view yet a further modification of the texturing or crimping apparatus of the present development, particularly as again concerns the taking-off or lifting means for the removal of the treated filament bundle from the texturing wheel;
FIG. 18 equally illustrates in fragmentary view a still further modification of the texturing or crimping apparatus of the present development, again with respect to the taking-off or lifting means for the removal of the treated filament bundle from the texturing wheel;
FIG. 19 illustrates on an enlarged scale part of the texturing or crimping apparatus, particularly the construction of the jet nozzle and its coaction with the texturing wheel;
FIG. 20 is a top plan view of the arrangement of FIG. 19;
FIG. 21 again illustrates on an enlarged scale, part of the texturing or crimping apparatus, particularly a modified construction of a jet nozzle and its coaction with the texturing wheel;
FIG. 22 illustrates on an enlarged scale and in fragmentary view a modified construction of the jet nozzle;
FIG. 23 illustrates on an enlarged scale and in fragmentary view, a further modified construction of the jet nozzle;
FIG. 24 illustrates on an enlarged scale and in fragmentary view, a still further modified construction of the jet nozzle; and
FIG. 25 illustrates on an enlarged scale and in fragmentary view, yet a further modified construction of the jet nozzle.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings, it is to be understood that to simplify the showing thereof, only enough of the structure of the texturing or crimping apparatus for continuously texturing or crimping thermoplastic filaments or filament yarns or threads has been illustrated therein as is needed to enable one skilled in the art to readily understand the underlying principles and concepts of the present invention. Turning now specifically to FIG. 1 of the drawings, the texturing or crimping apparatus illustrated therein by way of example and not limitation will be seen to comprise a jet nozzle or nozzle means 1 for injecting or introducing a filament bundle 2 together with a heated medium, such as preferably air, but also possibly steam or mixtures thereof, into an annular or ring-shaped stuffing chamber or compartment 3 which can be appropriately rotated and driven. The stuffing chamber 3 has an inlet or injection or receiving zone A for receiving and crimping the filament bundle 2, a treatment or heat transfer zone B for heating or cooling the crimped filament bundle 2.1 and a delivery or outlet zone C for delivering the crimped filament bundle 2.1 to a conveying element which in this case, for instance, is a suction drum or drum member 4 rotatable and drivable by means of a driven shaft 38. In order to transfer the crimped filament bundle 2.1 to the suction drum 4, there is shown a filament bundle-lifting or taking-off means 19 which will be considered in greater detail hereinafter.
The stuffing chamber 3 is disposed on the periphery or circumference of a texturing wheel or roller 5 mounted by means of a driven shaft 6 so as to be rotatable and drivable. The drive is not part of the invention and thus need not be here considered, particularly since a conventional drive can be used.
FIG. 2 depicts a modified construction of the texturing or crimping apparatus and shows the same elements as FIG. 1 except for the jet nozzle which is here somewhat different in design. This jet nozzle 1.1 of the embodiment of FIG. 2 has, as compared with the generally linearly extending jet nozzle 1 of the embodiment of FIG. 1, a bent or flexed outlet part or portion 11.1 as is shown in an enlarged scale in FIGS. 21 through 25. The advantage of the bent outlet part 11.1 is that the jet nozzle 1.1 can extend substantially radially towards the stuffing chamber 3 but nonetheless, the outlet part 11.1 can be arranged tangentially thereto, something which has advantages in terms of the arrangement or spatial layout.
Another advantage is that because of the bent walls 17.1 and 18.1 as shown, for instance, in FIG. 21, the filament bundle 2.1 which is guided and conveyed in the fiber or filament-guiding passage or duct 14 bounces or deflects at the bent wall 18.1, defining a deflecting plate or deflector, and is thus subjected to pre-crimping in addition to the pre-crimping produced by the escape of the fluid or gaseous medium, here typically air from the fiber or filament-guiding passage or duct 14 near the outlet part 11 and because of the friction prevailing between the filament bundle 2.1 and the bent walls 17.1 and 18.1.
In the embodiments herein disclosed where the jet nozzle has a bent outlet part, this bent outlet part, such as the bent outlet part 11.1 shown in FIG. 21, can enclose an angle of, for instance, about 90° to 170° with respect to the lengthwise axis of the substantially linear extending fiber or filament-guiding passage, such as the fiber or filament-guiding passage or duct 14 shown in FIG. 21.
Also, FIG. 3 shows a variant of the arrangement of FIG. 2, wherein here there is provided a roll pair 34 for taking over the textured or crimped filament bundle 2.1 instead of there being used the suction drum 4. Basically, just a single conveying roll could be provided instead of the roll pair 34.
FIG. 3 also differs from the embodiment of FIGS. 1 and 2 in that in FIG. 3, the filament bundle-lifting or take-off means 19 are not used; instead, the roll pair 34 removes the filament bundle 2.1 from the stuffing chamber 3.
The arrangements of FIGS. 1, 2 and 3 show near the treatment or heat transfer zone B, a blow-in device or means 35 for blowing a gaseous treatment medium into the stuffing chamber 3 for treating the crimped filament bundle 2.1 therein with heat and/or cold. In addition to the means 35, additional or second means 35.1, shown in FIG. 3, having the same function can be provided. In this event, the first means 35 are used to heat the crimped filament bundle 2.1 in the stuffing chamber 3 and the additional or second means 35.1 are used to cold treat such filament bundle 2.1.
The additional or second means 35.1 are mainly used when, as shown in FIG. 3, there is not provided any suction drum 4 on which the textured or crimped filament bundle 2.1 can be further cooled and which is located downstream of the texturing wheel or roller 5 as has been shown for the embodiments of FIGS. 1 and 2.
The suction drum 4 depicted in FIGS. 1 and 2 has, for example, on its periphery or circumference, a screen surface or sieve 4a through which air can be sucked near the suction passage 36.
The filament bundle-lifting or taking-off means 19 also can, of course, be used with the variant embodiment shown in FIG. 3. The difference between the use of the suction drum 4 as in the arrangements of FIGS. 1 and 2 and the use of a roll pair 34 as in the arrangement of FIG. 3, is that the crimped filament bundle 2.1 can be transferred automatically to the suction drum 4 by means of the filament bundle-lifting or taking-off means 19, whereas the crimped filament bundle 2.1 in the arrangement of FIG. 3 must be transferred by means of a suction nozzle or equivalent structure in order to be able to deposit the crimped filament bundle 2.1 on the roll pair 34. The filament bundle-lifting means 19 are therefore usually unnecessary with such arrangement.
As illustrated in FIGS. 5 and 5a, the stuffing chamber 3 comprises two fluid or air-pervious annular or ring-shaped walls or wall means 7 and 8 disposed on the texturing wheel or roller 5 and spaced at a distance D from one another. In this example, the walls 7 and 8 are constituted by two respective needle or pin rows embodied by adjacent individual needles or pins 9 or equivalent structure inserted or embedded into the periphery or circumference of the texturing wheel or roller 5. That part or portion of the periphery or circumference of the texturing wheel 5 which is disposed between the needle rows of the walls 7 and 8, forms the base or floor 10 of the stuffing chamber 3.
At this point, it is remarked that in FIGS. 19 and 20 there have been shown on an enlarged scale, the stuffing chamber or compartment 3 with the rows of needles 9 forming the walls 7 and 8 and the jet nozzle 1 whose outlet part or mouth portion 11 extends between the walls 7 and 8.
As will be seen from an inspection of FIGS. 19 and 20, the jet nozzle 1 comprises a filament entry or infeed orifice or port 12 through which the filament bundle 2 enters the jet nozzle 1 and with a fluid medium, such as an air infeed opening or aperture 13 through which a suitable pressurized fluid or gaseous medium, such as air, for instance, enters the fiber or filament-guiding passage or duct 14 through which the filament bundle 2 is guided and conveyed and which has entered through the filament infeed orifice 12.
The jet nozzle 1 is formed in its outlet part or mouth portion 11 with two recesses or openings or cutouts 15 and 16 which impart to such outlet part or portion 11 a width d corresponding at the maximum to the width D of the stuffing chamber 3 as has been illustrated in FIG. 20. These two recesses or openings 15 and 16 expose or free the fiber or filament-guiding passage or duct 14 in the outlet part or portion 11 over a length L visible in FIG. 19 such that the gaseous or fluid medium introduced into the fiber or filament-guiding passage or duct 14 can escape at least to some extent to atmosphere near such outlet part or portion 11. Because of such escape or efflux of the gaseous medium along the passage length L, the filament bundle 2 guided therein, starts to rub against the two other oppositely situated walls 17 and 18 because of the loss of at least some of the conveying medium, so that the speed of conveyance of the filament bundle 2 is reduced or retarded leading to stuffing of such filament bundle and, therefore, to pre-crimping in this part of the passage or channel.
FIGS. 4, 4a, 6 and 7 each show a variant of the texturing wheel or roller 5 of FIG. 5. The texturing wheel 5.1 and the stuffing chamber 3.1 of FIG. 4 have, instead of the needle row walls 7 and 8, perforated walls 7.1 and 8.1 formed with continuous or open-ended bores 27 and defining discoid rings. Some of these continuous bores 27 are shown in FIGS. 4 and 4a and serve the same purpose as the spaces or gaps between the needles 9 which allow for the escape of the air or fluid medium.
To facilitate removal of the crimped filament bundle 2.1 in the delivery zone or region C between the perforated walls 7.1 and 8.1, the same can, as shown in FIG. 4b, have an opening angle or aperture angle B (beta).
FIG. 6 shows as a variant construction, instead of the needles 9, radial teeth 28 which form the walls 7.2 and 8.2 and the stuffing chamber 3.2.
The radial teeth 28 are part of a tooth ring 29 drawn on to the texturing wheel 5.2 so as to be slip-free for operation. In the embodiment of FIGS. 6 and 6a, the teeth 28 are shown to constitute radial teeth.
FIGS. 7 and 7a also show two tooth rows 7.3 and 8.3 which form the stuffing chamber 3.3. In this case, however, the teeth 30 extend axially with respect to the driven shaft 6 as can best be gathered from FIG. 7a.
FIG. 8 illustrates an enlarged partial view along the section lines 5--5 of FIG. 5 and shows the walls 7 and 8 which are formed by the needles 9 and between which extends the outlet part or mouth portion 11.
As can be seen from FIG. 8, that part of the fiber or filament-guiding or conveying passage or duct 14 which belongs to the outlet part or portion 11 extends between the bounding walls 7 and 8 such that, as generally indicated in FIG. 1, the filament bundle 2 is introduced into the stuffing chamber 3 approximately half-way up the radial wall height H (FIG. 8) which laterally bounds the stuffing chamber 3.
The crimped filament bundle 2.1 adhering or clinging to the needles 9 of the walls 7 and 8 remains at this intermediate level and is positively guided in this position through the treatment zone or region B and also into the delivery zone or region C.
In the delivery zone C, the fiber bundle-lifting or taking-off means 19 extend between the walls 7 and 8 and desirably below the crimped fiber filament bundle 2.1 retained thereby.
At this point attention is directed to FIG. 9 in which a variant of the walls 17 and 18 of FIG. 8 is shown. In such FIG. 9, the oppositely situated walls 17.1 and 18.1 each have a concavity or concave configuration affording improved guidance of the crimped filament bundle 2.1 in the outlet part or portion 11.
FIG. 10 shows a variant of the needles 9 and of the use of the outlet part or portion 11 according to FIG. 8. Here the needles 9.1 shown in FIG. 10 are resilient and biased into engagement with the outlet part or portion 11. Such engagement is represented diagrammatically in FIG. 10 by the curved parts E and G. The braking effect provided by this friction between the needles 9.1 and the outlet part or portion 11 can be reduced at least to some extent by the finish which is present on the filament bundle 2 and which is transferred to some extent to the outlet part or portion 11. In this way, there can be reduced abrasion between the needles 9.1 and the outlet part or portion 11.
Also, FIG. 11 shows a variant of the arrangement of the needles or pins 9 and 9.1, respectively, as compared with that of FIG. 5. Here the needles 9 or 9.1 are inclined to the rear as considered with respect to a predetermined direction of rotation R of the texturing wheel or roller 5. This needle inclination is represented by the angle α and must be determined in dependence upon needle length, texturing wheel diameter and the arrangement of the fiber bundle-lifting or taking-off means 19. The needle inclination should be such as to facilitate the lifting-out of the crimped filament bundle 2.1.
In FIG. 12 and as compared with the previous illustrated constructions in which two rows of spaced needles are used to form the spaced-apart walls 7 and 8, here a double row of needles 9 is used for each wall 7.4 and 8.4. As such FIG. 12 shows, the two adjacent rows of needles 9 forming any one wall 7 and 8 are staggered relative to one another.
FIG. 13 shows another variant construction wherein the walls 7.5 and 8.5 are each constituted by one row of needles 9 and a respective perforated annular or ring-shaped disc 23 and 24 which provides an at least partial closure or enclosure of the stuffing chamber 3 towards the outside, i.e., radially of the texturing wheel or roller 5. The partial closure arises because the two perforated annular or ring-shaped discs 23 and 24 can be selectively moved in the peripheral direction as indicated by the double-headed arrows K and M, respectively, so that the continuous apertures or bores 25 in the perforated annular or ring-shaped discs 23 and 24 are to some extent in alignment with the needles 9 and thus restrict the passage of air between the needles 9 to a given extent. The possibility that the perforated annular discs 23 and 24 can be rotated in the peripheral directions K and M, respectively, provides at least partial control of venting of the crimped filament bundle 2.1 disposed between the needle rows.
FIG. 14 shows a variant of the needle rows from the arrangement of FIGS. 5 and 5a and FIGS. 8 through 10, respectively, with lamellae or narrow plates 26 or equivalent structure being used instead of the heretofore described needles. The advantage of using lamellae 26 is that from the production standpoint, it is simpler to form slots in the texturing wheel or roller 5 instead of the fine bores necessary for receiving the needles 9. Also, the lamellae 26 or the like can be resilient so that, in response to the lifting of the crimped filament bundle 2.1 in the lifting or take-off region or zone, they experience, in a manner similar to that shown in FIG. 11, by virtue of the lifting of the crimped filament bundle 2.1, a bending action or flexing facilitating the lifting-out or take-off of the crimped filament bundle 2.1.
Details of various possible constructions of the fiber or filament bundle-lifting or taking-off means 19 are shown in FIGS. 15 through 18. The filament bundle-lifting means 19 shown in FIG. 15 are in the form of an endless belt 19.1 which runs on the stuffing chamber base or floor 10 and is deflected around a deflecting roll or roller 20. The endless belt 19.1 lies flush on the base or floor 10 and is therefore moved by the texturing wheel or roller 5 without slip. This endless belt 19.1 departs from between the two mutually spaced air pervious walls of the associated stuffing chamber 5, 5.1, 5.2 or 5.3.
FIG. 16 shows a stationary lifting wedge or wedge means 19.2 which terminates substantially tangentially with respect to the stuffing chamber base or floor 10 and which is rigidly connected to a fixed part or portion 21 of the machine frame. This stationary lifting wedge 19.2 has a substantially planar fiber-guiding surface 19a.
FIG. 17 also shows a stationary lifting wedge or wedge means 19.3 which is secured to the machine part 21 and has a convexity or concave portion 22 at the end near the texturing wheel or roller 5 to thus define a curved fiber-guiding surface.
FIG. 18 shows as the fiber or filament bundle-lifting or taking-off means, a lifting nozzle 19.4 which can eject compressed air in the conveying direction F in order to lift away from the stuffing chamber walls or wall members 7 and 8, the crimped filament bundle 2.1 disposed above the lifting nozzle and to supply such crimped filament bundle 2.1 to the next conveyor or outfeed structure or the like.
This lifting air nozzle 19.4 is rigidly connected to the machine part 21 and has a compressed air connection 37 for compressed air, generally indicated by the arrow.
The air ejected in the conveying direction F issues from appropriate apertures or openings, generally indicated by reference character 19b which are either disposed in an appropriate end zone or terminal region of the lifting nozzle 19.4 or are embodied by forming the lifting air nozzle 19.4 of a very porous material.
At this juncture it is remarked that FIG. 22 shows another construction of the outlet part or portion 11 and 11.1 previously considered. Here the outlet part or portion 11.2 is additionally formed with, for instance, an air exit or outflow opening or passage 31 connected to a compressed air connection 32 so that compressed air can enter the outlet part or portion 11.2 in the direction of the filament bundle 2.1 issuing from the outlet part 11.2. This compressed air can be used to control the aforedescribed bouncing or deflection of the filament bundle 2.1 at the bent wall 18.1. The fluid medium entering through the exit or outflow opening 31 can be the same or different than the heated medium flowing through the passage or channel 14.
FIG. 23 shows a construction similar to FIG. 22. However, here there is no bent or deflecting wall 18.1 but there is an air exit aperture or opening or passage 31.1 which, like the air exit opening or passage 31, blows or issues towards the filament bundle 2.1 conveyed by the filament-guiding passage or duct 14 in order to deflect the filament bundle 2.1 without any bouncing at the bent wall 18.1.
FIG. 24 shows the jet nozzle 1.1 with an outlet part 11.4 differing from the outlet part or portion 11.1 of the arrangement of FIG. 21 by here having a radius N in the wall 18.2 to define a rounded portion or transition region. This radius provides an alternative form from the air stream of FIG. 22 for controlling the bouncing effect of the bent wall 18.2.
FIG. 25 shows a further variation of the outlet part or portion 11.1 of FIG. 21 in that here the outlet part or portion 11.5 of FIG. 25 has needle walls 17.2 and 18.2 instead of the respective walls 17.1 and 18.1 of FIG. 21. The needle walls 17.2 and 18.3 of FIG. 25 are embodied by adjacently arranged needles or pins 33 with a small space or gap disposed between the individual needles 33 so that the air conveyed by the filament-guiding or conveying passage or duct 14 can escape near the spaced needles 33 in order to produce further pre-crimping of the filament bundle 2.1 near these needles 33. As in the variants shown in FIGS. 21 to 24, the first pre-crimping is produced in that passage part of the outlet part or portion which forms a continuation of the filament-guiding passage or duct 14.
The outlet parts or portions 11.1, 11.2, 11.3, 11.4 and 11.5 of FIGS. 21 through 25 are formed with not particularly referenced recesses or openings corresponding to the aforediscussed recesses 15 and 16 in order to free or expose the filament-guiding or conveying passages 14 having the width d as shown in the drawings.
The invention can be used, for example, for the texturing or crimping of polyamide 6 and 66 and for polypropylene. It has been found by experience that for a filament bundle of 500 to 3,000 d tex there can be employed a distance D (FIG. 20) of 3 to 4.5 mm and a cross-section of the filament-guiding or conveying passage or duct 14 of from 10 to 20 mm 2 , respectively.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. ACCORDINGLY,
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For continuously crimping thermoplastic filaments, a filament bundle is blown by a jet nozzle into a stuffing chamber of a texturing wheel to produce a crimped filament bundle in the stuffing chamber. The stuffing chamber has a receiving zone, a treatment zone and a delivery zone. The filament bundle is subjected to a texturing or crimping treatment in the receiving zone and, depending upon the fiber material to be processed, undergoes a heating or cooling treatment in the treatment zone. The heating or cooling treatment is accomplished by a blowing agent which blows a gaseous medium into the stuffing chamber. At the delivery zone, the crimped filament bundle is taken-off or lifted-out of the stuffing chamber by fiber bundle-lifting means and moved towards a suction drum receiving the filament bundle. The reception of the crimped fiber bundle at the suction drum is assisted by a suction passage in the suction drum which sucks air through a porous surface thereof so that the filament bundle remains adhering to such suction surface and is further cooled by the ambient air. The texturing wheel and the suction drum are rotatably and drivably mounted.
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PRIORITY CLAIM
Not Applicable
CROSS-REFERENCE TO RELATED ARTICLES
[1] Load Pull System: http://www.microwaves101.com/encyclopedia/loadpull.cfm
[2] S-parameter Basics: http://www.microwaves101.com/encyclopedia/sparameters.cfm
[3] U.S. Pat. No. 6,674,293 Adaptable pre-matched tuner system and method
[4] U.S. Pat. No. 7,135,941 Triple probe automatic slide screw load pull tuner and method
[5] Coaxial Circulators: http://www.dpvrf.com/Coaxial_Circulators.html
[6] Directional Couplers: http://www.e-meca.com/rf-directional-coupler/directional-coupler-780.php
[7] Frequency Diplexers: http://www.markimicrowave.com/2781/Diplexers.aspx
[8] Low pass filters: http://www.markimicrowave.com/3448/Low_Pass_Filters.aspx
[9] MPT, a universal Multi-Purpose Tuner, Product Note 79, Focus Microwaves, October 2004
[10] Active load pull system: http://ieeexplore.ieee.org/xpl/freeabs_all.jsp?arnumber=1516920
[11] Harmonic Active Injection Load Pull, HAILP; datasheet, Focus Microwaves, 2011
[12] U.S. patent application Ser. No. 12/929,643: Method for Calibration and tuning with Impedance tuners
[13] Frequency Diplexers: http://en.wikipedia.org/wiki/Diplexer
[14] Wideband phase shifters: http://www.pasternack.com/phase-shifter-frequency-range-265-400-ghz-pe8249-p.aspx
BACKGROUND OF THE INVENTION—PRIOR ART
This invention relates to high power (nonlinear) testing of microwave transistors (DUT) in the frequency and time domain [1]. The electrical signals injected into the input of the DUT and extracted from the output can be measured using sampling devices, such as signal couplers [6]. At high power the (nonlinear) DUT is saturating and deforming the sinusoidal input signal. As a result part of the power is contained in harmonic frequency components. The DUT performance can only be optimized when all harmonic frequency components are impedance-matched properly. This requires independent harmonic tuning, mainly but not exclusively, at the DUT output.
Load pull is the method by which the load impedance presented to the DUT at a given frequency is changed systematically and the DUT performance is registered, with the objective to find an optimum depending on the overall design objectives [1]. This may be maximum power, efficiency, linearity or else. The same is valid for the source side of the DUT. Passive (slide screw) tuners are used to emulate the various impedances presented to the DUT [3]. Insertion loss in the signal path between the DUT and the tuner reduce the “tuning range” of the tuner and it often happens that the DUT cannot be matched properly, if its internal impedance cannot be reached by the tuner (reduced by the insertion losses of the transmission section between tuner and DUT). In these cases “active load pull systems” can be used [10].
Active load pull systems use amplifiers in an “open” or “closed” loop configuration to recover and re-inject part of the outgoing power into the DUT in order to generate a “virtual” load. Depending on the gain and power of the amplifiers in the loops the returning power can be equal or even higher than the outgoing power, so the virtual reflection factor δ, defined as |Γ| 2 =Pr/Pi, where Pr is the power reflected by the load and Pi the power delivered by the DUT, presented to the DUT can be equal or even higher than 1. The subject of this invention is to introduce a component which allows controlling the amplitude and phase of the signals returned to the DUT by the “active” loop.
In the case of open loop active load pull systems there are, in principle, two ways for injecting signal power at controlled amplitude and phase into the DUT. One is by using external synchronized signal sources at the designated (harmonic) frequencies and the other is to use closed loops and control amplitude and phase individually [11]. This second option requires a “frequency selective amplitude and phase controller”. Such an apparatus is presented here.
A device capable of controlling the amplitude and phase of signals in the microwave frequency range individually for a number of frequencies is not known. What is known are commercially available variable attenuators ( FIG. 1 ) and phase shifters ( FIG. 2 ). Whether those components are manually or remotely controlled is irrelevant. What is important is that they are “wideband”; this means the amplitude and phase of two signals with different frequencies going through those components cannot be controlled independently. This makes those components useless for the present application.
The present invention describes an apparatus that can do that; it can adjust, independently, the amplitude and phase of a number of signals at different frequencies passing through it.
DESCRIPTION OF THE DRAWINGS
The present invention will be better understood in view of the enclosed drawings of which
FIG. 1 depicts prior art: a commercially available wideband variable attenuator.
FIG. 2 depicts prior art: a commercially available wideband variable phase shifter.
FIG. 3 depicts a basic (non-frequency selective) amplitude and phase modulator using a circulator and a wideband impedance tuner.
FIG. 4 a ) and b ) depict the tuner reflection factor and the associated modulator transmission factor of the apparatus in FIG. 3 .
FIG. 5 depicts an octave band covering amplitude and phase modulator using an octave band circulator and a two-probe two-frequency impedance tuner.
FIG. 6 depicts an octave band covering amplitude and phase modulator using an octave band circulator and a three-probe three-frequency impedance tuner.
FIG. 7 depicts an actual implementation of an apparatus as described in FIG. 3 .
FIG. 8 a ) and b ) depict measured results on the frequency selective control of the transmission factor S 31 (Fo), created by the associated tuner reflection factor S 11 (2Fo) or Γ(2Fo); note that when a twoport is terminated with the characteristic impedance (Zo=50Ω), then S 11 =Γ.
FIG. 9 depicts a wideband (more than one octave) attenuator/phase modulator using two circulators, three power dividers/combiners and a three-probe multi frequency impedance tuner.
FIG. 10 depicts the implementation of the apparatus in FIG. 9 , using additionally two high/low pass filters for better signal frequency band separation.
FIG. 11 depicts the implementation of the apparatus of FIG. 9 , where one power combiner/divider is replaced by a frequency diplexer.
FIG. 12 depicts an implementation of the apparatus in FIG. 9 , whereby high/low pass filters ensure better signal frequency band separation.
FIG. 13 depicts the implementation of the apparatus of FIG. 9 , whereby high/low pass filters and a frequency diplexer ensure better signal frequency band separation.
FIG. 14 depicts the implementation of the apparatus of FIG. 9 , whereby two power dividers are replaced by frequency diplexers for better signal frequency band separation.
DETAILED DESCRIPTION OF THE INVENTION
The proposed apparatus utilizes the capacity of wideband multi-carriage electro-mechanical impedance tuners to synthesize user defined reflection factors (impedances) covering the whole Smith chart for a number of frequencies individually and independently [3, 4, 9, 12]. The tuners have a test port and an idle port and are, typically, terminated at their idle port with the characteristic impedance (typically Zo=50Ω) or an impedance close to it; their test port is connected to one port of a circulator (typically port 2 ), FIG. 3 ; the signal is injected into the previous circulator port, following the signal flow (typically port 1 ). In this case the signal frequencies are reflected (Γ) at the test port of the tuner and re-injected into port 2 to exit at the last circulator port (typically port 3 ).
The signal transmission factor A 31 between port 1 and port 3 ( FIG. 3 ) is then directly proportional to the reflection factor Γ at port 2 . Since the wideband tuner can synthesize any reflection factor Γ(F)=|Γ*exp(jφ) in amplitude and phase for any pre-calibrated frequency (F), within the tuning rang of the tuner, at will, so will do the complex transmission factor A 31 . A 31 is defined as the ratio of the signal vector at port 3 (V 3 =|V 3 |*exp(jφ 3 ) divided by the signal vector at port 1 (V 1 =|V 1 |*exp(jφ 1 )):
A 31= V 3/ V 1=| V 3|/| V 1|*exp( j (φ3−φ1)). eq(1)
If ports 1 and 3 are terminated with the characteristic impedance (Zo) then the general transmission factor A 31 becomes (by definition) equal to the scattering parameter S 31 (A 31 =S 31 ) [2]. In network terms and in the case of a circulator, if the transmission parameter between ports 1 and 2 is S 21 and between ports 2 and 3 is S 32 , and the reflection factor of the tuner, connected at port 2 , is Γ=|Γ|*exp(jφ), then the overall transmission parameter S 31 is:
S 31= S 21* T*S 32, (eq. 2)
or
| S 31|=| S 21|*|Γ|*| S 32|
and
φ31=φ21+φ+φ32 (eq. 3)
Equations (2) and (3) are valid only in case of circulators and inside the operation frequency of the circulators, since in this case the reverse transmission factors are equal to or close to zero: S 12 ≈S 23 ≈S 13 ≈0, whereas in the forward direction their amplitudes are all close to one: |S 21 |≈|S 32 |≈|S 31 |≈4.
Since both amplitude and phase of the transmission s-parameters S 21 and S 32 of the circulators are component-specific and not affected by the tuner movement, then it is obvious that the amplitude and phase of the overall transmission S 31 depends only of Γ=|Γ|*exp(jφ), whereas |Γ| is the magnitude and φ the phase of the reflection factor at the tuner test port (connected to port 2 of the circulator, FIG. 3 ). Therefore for frequencies inside the operation bandwidth of a typical circulator the apparatus is providing the expected result ( FIG. 4 ). FIG. 4 a ) shows the reflection factor which the tuner presents connected to port 2 of the circulator and FIG. 4 b ) shows the associated transmission factor S 31 . A reflection factor of zero ( 41 ) generates a transmission factor of zero as well ( 42 ); this is because all power injected into port 1 of the circulator and transmitted to port 2 is absorbed by the characteristic impedance Zo seen through the tuner, since the probes of said tuner are fully withdrawn and the tuner represents, in that case, a simple transmission line. A medium level reflection factor ( 43 ) creates a medium level transmission factor ( 44 ) as well; shifting the reflection factor ( 43 ) to ( 45 ) by moving the tuner probes horizontally along the axis of the slabline, also shifts the transmission factor ( 44 ) to ( 46 ) by the same angle. A maximum tuner reflection factor ( 47 ) generates also a maximum transmission factor ( 48 ). Because of this equivalence calibrating the amplitude/phase controller is following the same algorithms and may use the same interpolation and tuning routines as the prior art impedance tuners themselves [3, 4, 12].
Circulators are components based on the anisotropy of magnets incorporated in them which attenuate the electro-magnetic field according to its polarization. Therefore the RF signal passes only in one direction (forward) and is attenuated, by a typical factor between 100 (20 dB) and 1000 (30 dB) in the opposite direction. Available circulators cover typically one octave (Fmax/Fmin=2) or less, especially at frequencies below 1 GHz. At higher frequencies octave bandwidths or even slightly more are available [5].
For applications where harmonic tuning is required, such as harmonic load pull, a standard octave band circulator will, therefore, allow operation only at the limits of its frequency range. For instance, a 2-4 GHz circulator will allow harmonic tuning only at Fo=2 GHz and 2Fo=4 GHz ( FIGS. 5, 7 ). Any frequency other than 2 GHz will not be operational. This is an important limitation. First of all tuning is typically required at 3Fo as well. Secondly most harmonic tuning applications are not identical with the typically available circulator octave bands. If Fo will be covered probably 2Fo and 3Fo will not. To solve this problem alternative configurations are needed. The apparatus of FIG. 6 , whereas it can control up to three frequencies independently, as far as they are inside the bandwidth of the circulator, it cannot control more than two harmonic frequencies, because of the circulator limitations, and this only when Fo and 2Fo fall exactly at the operation limits of the circulators. FIG. 8 a ) shows the tuner reflection factor and FIG. 8 b ) the transmission factor at Fo and 2Fo in an application, in which the two-harmonic tuner in FIG. 7 controls independently amplitude and phase of the transmission factor S 31 (Fo) and S 31 (2Fo). Whereas S 31 (Fo) can be kept constant, S 31 (2Fo) can be tuned to any area of the Smith chart (within the “tuning” range of the tuner). In this case Fo and 2Fo are chosen to be at the operation limits of the octave band circulator used (Fo=2 GHz, 2Fo=4 GHz).
To overcome the bandwidth limitations of circulators, alternative configurations require the use of octave band circulators in parallel, where the signal is split and injected into the adjacent circulators before reaching the wideband harmonic tuner ( FIGS. 9-14 ). Assuming two octave band circulators, such as 2-4 GHz and 4-8 GHz, the new configurations will be able to process signals from Fo=2 GHz to 4 GHz for controlling Fo and 2Fo or from 2 GHz to 2.66 GHz for controlling Fo, 2Fo and 3Fo. This approach is valid throughout the frequency range of available circulators [5]. In order to do so the RF signal must be split before reaching the adjacent circulators, be combined before reaching the test port of the multi-probe tuner, then be split again before being injected into the second port of the circulators and finally be re-combined at the output of the network ( FIGS. 9-14 ). The frequency splitting can be performed either using the frequency selective transmission behavior of the circulators ( FIG. 9 ), which is not a very effective approach, or (more effectively, but also more coumbersome and expensive) by using low-pass/high-pass filter combinations or frequency diplexers ([7, 8, 13], FIGS. 10-14 ). For ultra-wideband applications additional frequency separation branches can be used, such as splitting the high frequency branch in two using additional filters/diplexers or using frequency triplexers to start with.
All configurations ( FIGS. 9-14 ) operate on the same principle; using the schematics of FIG. 9 : the incoming signals (A) are separated in bandwidths associated with the bandwidths of the following circulators (B, H). The corresponding signals then enter ports (B′, H′) of said circulators and exit ports (C, F) of the same. Then said signals are combined through power combiners (C′, F′) into the test port of a wideband multi-harmonic tuner (E), which reflects each signal frequency Fi with a distinct, user defined, reflection factor Γ(Fi), preset at port E; then the reflected signal follows its way back through the combiner into the ports (from E to C′/C, and from E to F′/F) of the associated circulators, and exit from said circulators at ports (D/D′, G/G′). The signals arriving at (D′, G′) from both circulators are then combined into the output port (J). Alternative configurations, in which combiners are replaced by combinations of low/high pass filters and/or frequency diplexers, are preferable from the point of view of better RF performance, but more complex and costly ( FIGS. 10-14 ); in any case the principle is the same.
Using frequency discriminators/filters in FIGS. 10-14 improve the practical separation among bands but they are themselves frequency limited. Using wideband power combiners/dividers relies on the frequency selectivity of said circulators, which may be insufficient to avoid signal combinations at the output and cross interference. This can only be decided, however, on a case by case situation, after the circulators have been fully characterized in view of the harmonic frequencies to be used and a cost/performance analysis has been carried through.
The invention describes the concept of a multi-frequency variable attenuator and phase shifter, in which each frequency is controlled independently; the concept has been shown experimentally also for one and two frequencies as well as for harmonic frequencies; the concept has been described in a number of embodiments; obvious alterations shall not limit or affect the validity of the innovation.
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A multi-frequency programmable and remotely controllable variable attenuator and phase shifter (MF-VAPS) network utilizes wideband three port circulators, power combiners, high-low pass filters and a calibrated multi-harmonic tuner to control the amplitude and phase of the transmission factor (A 21 ) at up to three user defined frequencies individually. The harmonic signal components are divided in frequency bands and injected into the circulator's port 1 and extracted from port 3 , whereas the tuner is connected to port 2 and terminated with Zo. When the tuner is initialized (S 11 =0) the transmission factor of the network is zero; when the tuner is at maximum reflection at any frequency the transmission factor is also maximum. Changing the reflection phase of the tuner controls the transmission phase <A 21 by the same amount, up to 360°.
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[0001] This application is a Continuation of U.S. application Ser. No. 09/573,007 filed May 18, 2000.
FIELD OF THE INVENTION
[0002] The present invention relates to improving computer-implemented auctions and, more particularly, to computer implementation of an efficient dynamic multi-unit auction.
BACKGROUND OF THE INVENTION
[0003] Auction formats in the art tend generally to be of the sealed-bid or ascending-bid variety. In the standard sealed-bid auction, bidders—in one single bidding round—simultaneously and independently submit bids to the auctioneer, who then determines the auction outcome. In the standard ascending-bid auction, bidders—in a dynamic bidding process—submit bids in real time until no more bids are forthcoming. An ascending-bid format offers the advantage that there is feedback between participants' bids: each bidder is able to infer other bidders' information about the value of the object(s) as the auction progresses and incorporate this information into his subsequent bids. This feedback tends to result in more efficient auction outcomes as well as more aggressive bidding, resulting in higher expected revenues for the seller.
[0004] However, standard ascending-bid formats—such as the design used by the Federal Communication Commission for auctioning radio communications spectrum—have the disadvantage that they do not generally lead to outcomes which are efficient in the sense of assigning objects to the bidders who value them the most. Most ascending-bid auction formats have the unfortunate property that identical objects sell at the uniform price reached at the end of the auction. This creates incentives for bidders to engage in demand reduction: bidders have incentive to understate the values that they place on marginal units in order to reduce the market-clearing price (and, hence, the price they will pay on the inframarginal units that they will win in any case). This has clear negative implications both for efficiency and for revenues.
[0005] My prior patent, “System and Method for an Efficient Dynamic Auction for Multiple Objects,” (U.S. Pat. No. 6,026,383, issued 15 Feb. 2000) provides an early version of a system and method for a dynamic auctions which may achieve efficiency for situations involving multiple identical objects. The current invention is an improved system and method for a dynamic multi-unit auction which may achieve efficiency in more general economic environments.
SUMMARY OF THE INVENTION
[0006] The present invention is a system and method for implementing on a computer a dynamic multi-unit auction in which the price paid or received by bidders tends to be independent of their own bids, in which participants may be provided with information concerning their competitors' bids as the auction progresses, and in which the confidentiality of high values is maintained. This provides the advantage of improving the economic efficiency of the auction design over the prior art. The present invention usefully enables a seller or buyer to efficiently auction multiple types of goods or services, and to efficiently auction items with complex possibilities for substitution.
[0007] The present invention comprises a computer that receives bids in a dynamic bidding process and assigns the items to bidders, and a method for receiving bids in a dynamic bidding process and assigning the items to bidders. In one embodiment, the invention comprises a bidding information processor (BIP) and a plurality of bid entry terminals (BET's) communicatively coupled to the bidding information processor. Bidders at the bid entry terminals enter bids in multiple rounds, and may observe displayed auction information. The bidding information processor and the bid entry terminals communicate and process information in order to conduct an auction.
[0008] Suppose that m (m≧1) types of objects are being auctioned, and one or more units of each type are being auctioned. An auction in accordance with an embodiment of the present invention proceeds as follows. First, the auctioneer (i.e., the bidding information processor) determines a starting price vector, (P 1 , . . . , P m ), and transmits it to bidders (i.e., bid entry terminals). Second, a bidder responds with a bid vector indicating the quantity of each respective type of object that the bidder wishes to transact at the current price vector. Let the bidders be superscripted by i, where i=1, . . . , n. The bid vector for bidder i is denoted by (Q 1 i , . . . , Q m i ). Also, let the quantities of the respective types of objects being auctioned be denoted by ({overscore (Q)} 1 , . . . , {overscore (Q)} m ). Typically, the aggregate quantity of each type of object desired by all the bidders (i.e., Σ i=1 n Q k i ) is greater than the quantity of each type of object being auctioned (i.e., {overscore (Q)} k ). In this event, the auctioneer still determines whether any of the objects should be assigned to any bidders in this round. This is done by determining for each bidder, separately, whether the sum of the quantities bid by all the other bidders for all m types of objects is less than the sum of the quantities of all m types of objects being auctioned. In other words, there is at least one object which is desired by only one bidder. In the event that the auctioneer determines a bidder who should be assigned objects, the auctioneer further determines which type(s) of objects should be assigned to such bidder. This is done by determining for each type of object, separately, whether the sum of the quantities bid for this type of object by all the other bidders is less than the sum of the quantities being auctioned. In other words, there is at least one object of this type which is desired by only one bidder. Those objects, of those types, are then assigned to that bidder, obligating that bidder to transact them at the prices standing for those types of objects at that time. (If more than one possible assignment vector to that bidder is consistent with this rule, then the auctioneer is permitted to select his most-preferred assignment vector consistent with this rule.) If any objects remain unassigned, the auctioneer announces a new price vector and the auction continues.
[0009] Certain constraints are desirable in order for this auction to operate optimally and to reach an economically efficient outcome. One exemplary constraint is an activity rule which constrains a bidder not to increase his quantity, summed over the m types of objects, from one round to the next. Another exemplary constraint is a more stringent activity rule which constrains a bidder not to increase his quantity, individually on each of the m types of objects, from one bid or one round to the next. A third exemplary constraint is a reduction rule which constrains a bidder not to decrease his quantity, for any single type of object, beyond the point where the sum of the quantities bid for this type of object by all bidders equals the sum of the quantities being auctioned. (If, in a given round, two or more bidders simultaneously attempt to decrease their quantities, for any single type of object, having the effect of reducing bids beyond the point where the sum of the quantities bid for this type of object by all bidders equals the sum of the quantities being auctioned, the auction procedure will resolve this discrepancy. For example, the auctioneer may honor these attempts to decrease in order of time priority, or may ration these simultaneous attempts to decrease in proportion to the attempted reductions.)
[0010] While an auction following these rules could be conducted manually, computerized conduct of the auction allows the auction to be conducted with all bidding information taken into account, while controlling the degree to which the information itself is disclosed to the participants. Computerized conduct of the auction also allows the auction to be conducted swiftly and reliably, even if bidders are not located on-site. The amount of information which is transmitted to the bid entry terminals and/or actually displayed to the bidders may be carefully controlled. In one embodiment, all bidding information is displayed to the bidders. In another embodiment, no bidding information is displayed to the bidders; only the results of the auction are displayed. A number of intermediate embodiments are also possible, in which some but not all bidding information is displayed to the bidders. For example, in one preferred embodiment, the auctioneer disclose only the aggregate quantity bid for each type of object in each round, as opposed to disclosing each individual bid.
[0011] My prior patent U.S. Pat. No. 6,026,383 treats auctions for multiple, identical objects and close substitutes. The earlier application's alternative auction—which may be viewed as a special case of the current auction design—exploited features of the homogeneous-good environment to construct an eminently-simple dynamic procedure. Unfortunately, the cases of multiple types of objects, or objects with complex possibilities for substitution, do not lend themselves to quite as simple a procedure. My other prior patents, “Computer Implemented Methods and Apparatus for Auctions,” U.S. Pat. No. 5,905,975, issued 18 May 1999, and U.S. Pat. No. 6,021,398, issued 1 Feb. 2000, describe other auction designs for multiple, dissimilar objects. However, the current auction design appears likely in practice to be simpler and to run more swiftly, as well as placing lower computational demands on bidders.
[0012] The present invention generalizes my auction design described in U.S. Pat. No. 6,026,383 to treat—in a simple way—the case of auctioning a set of items which includes two (or more) items that are neither identical nor perfect substitutes to one another. Henceforth, this will be described for short as a situation with “multiple types of multiple objects,” or simply “heterogeneous items” or “heterogeneous objects.” Often, but not always, the heterogeneous items auctioned together will bear some relationship to one another: for example, they may be licenses or rights to perform essentially the same activity at different geographic locations; or they may be securities issued by the same entity but with different durations to maturity; or they may be related goods with slightly different characteristics that render them only imperfect substitutes.
[0013] The present invention may also be better suited than previous auction designs for treating the case of identical objects or perfect substitutes which exhibit “increasing returns” for bidders. “Increasing returns” refers to a situation where the extra value that a bidder derives from an (N+1) st unit is greater than the extra value that a bidder derives from an N th unit. For example, this would include a situation where the utility from two units is strictly more than double the utility derived from one unit.
[0014] The present invention is useful for conducting auctions involving objects offered for sale by the bidders, as well as objects offered for sale to the bidders. Although terms such as “vector of quantities demanded” (by a bidder) and “demand curve” (of a bidder) are used to describe the present invention, the terms “vector of quantities offered” (by a bidder) and “supply curve” (of a bidder) are equally applicable. In some cases, this is made explicit by the use of both terms, or by the use of the terms “vector of quantities transacted” (by a bidder) and “transaction curve” (of a bidder). The term “quantities transacted” includes both “quantities demanded” and “quantities offered”. The term “bid” includes both offers to sell and offers to buy. The term “transaction curve” includes both “demand curve” and “supply curve”. Moreover, any references to “quantities being offered” includes both “quantities being sold” by the auctioneer, in the case this is an auction for selling objects, as well as “quantities being bought or procured” by the auctioneer, in the case this is an auction for buying objects or procuring objects.
[0015] Moreover, while standard auctions to sell typically involve ascending prices, the present invention may utilize prices that ascend and/or descend. One useful situation in which the price would be allowed to descend is a procurement auction or “reverse auction,” an auction to buy.
[0016] Throughout this document, the terms “objects”, “items”, “units” and “goods” are used essentially interchangeably. The inventive system may be used both for tangible objects, such as real or personal property, and intangible objects, such as telecommunications licenses or electric power. The inventive system may be used in auctions where the auctioneer is a seller, buyer or broker, the bidders are buyers, sellers or brokers, and for auction-like activities which cannot be interpreted as selling or buying. The inventive system may be used for items including, but not restricted to, the following: public-sector bonds, bills, notes, stocks, and other securities or derivatives; private-sector bonds, bills, notes, stocks, and other securities or derivatives; communication licenses and spectrum rights; clearing, relocation or other rights concerning encumbrances of spectrum licenses; electric power and other commodity items; rights for terminal, entry, exit or transmission capacities or other rights in gas pipeline systems; airport landing rights; emission allowances and pollution permits; and other goods, services, objects, items or other property, tangible or intangible. It may be used in initial public offerings, secondary offerings, and in secondary or resale markets.
[0017] The communication system used, if any, can be any system capable of providing the necessary communication and includes for example a local or wide area network such as for example ethernet, token ring, or alternatively a telephone system, either private or public, the Internet, the Worldwide Web or the information superhighway.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is an exemplary block diagram of an auction system in accordance with the invention;
[0019] FIG. 2 is a detail of one element of the system of FIG. 1 ;
[0020] FIG. 3 is a flow diagram of an auction process in accordance with one embodiment of the invention;
[0021] FIGS. 4 a, 4 b, and 5 are more detailed flow diagrams illustrating, in more detail, elements of the diagram of FIG. 3 ;
[0022] FIG. 6 is a flow diagram of an auction process in accordance with another embodiment of the invention;
[0023] FIG. 7 is a flow diagram of an auction process in accordance with another embodiment of the invention; and
[0024] FIGS. 8 a, 8 b, 8 c and 9 are more detailed diagrams illustrating elements of an earlier diagram.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0025] The drawings of FIGS. 1-4 of my prior patent U.S. Pat. No. 6,026,383 and of FIGS. 1-12 of my patent U.S. Pat. No. 5,905,975, and the associated text, provide a general superstructure for the present auction method and system, especially as it relates to the computer implementation thereof. Moreover, the terminology established in the previous applications will be relied upon as needed. The following description will detail the flow of the novel features of the preferred embodiments of the present method and system for an efficient dynamic auction for multiple types of multiple objects.
[0026] Before describing how the auction process is implemented, reference is made to FIG. 1 to describe an exemplary block diagram of one embodiment of the a system in accordance with the present invention. As illustrated in FIG. 1 , the auction system includes an auctioneer's system 10 (sometimes also referred to as a Bidding Information Processor or BIP) and a plurality of user systems 20 a, 20 b and so on (sometimes also referred to as Bid Entry Terminal or BET), each user system 20 a, etc. represents an individual bidder. The systems 10 - 20 n are communicatively interconnected via a communication system represented by the illustrated connections. The communication system can represent any system capable of providing the necessary communication to/from BIP and BET and includes for example a local or wide area network such as for example ethernet, token ring, or alternatively a telephone system, either private or public, the internet, the worldwide web or the information superhighway. Each of the systems 10 - 20 n includes a typical user interface 15 , 25 a for input/output and can include a conventional keyboard, display, and other conventional I/O devices. Within each of the systems, the user interface ( 15 , 25 a, etc.) is coupled to a communication interface ( 14 , 24 a, etc.) which is in turn connected to the communication system. Both the user interface and communication interface are also connected, at each system, to a CPU ( 12 , 22 a, etc.). Each system includes a memory ( 16 , 26 a, etc.) which can further be broken down into a program partition ( 17 , 27 a, etc.), a data partition ( 18 , 28 a, etc.) and an operating system partition ( 19 , 29 a, etc.). In each system the CPU ( 12 , 22 a, etc.) represents a source of intelligence when executing instructions from the memory ( 16 , 26 a, etc.) so that appropriate input/output operations via the user interface and the communications interface take place as is conventional in the art. The particular steps used in implementing the inventive auction system are described in more detail below. In one embodiment, each of the systems are personal computers or workstations.
[0027] FIG. 2 is a more detailed illustration of an exemplary BIP 10 showing details of the data partition 18 . As seen in FIG. 2 the data partition includes provision for creating, storing, processing and outputting values representing Current Lot Number 18 - 1 , Current Round Number 18 - 2 , Current Price 18 - 3 , List of Bidder Numbers 18 - 4 , Bidding History 18 - 5 , Constraints on Bids 18 - 6 , Passwords, 18 - 7 and Current Objects Available 18 - 8 . The particular set of data required for any particular auction and the format of that datum or data (such as scalar, vector, list, etc.) is more particularly specified by the detailed description of that auction.
Embodiments Concerned with Complex Possibilities for Substitution
[0028] Some of the simplest embodiments of the present invention apply in situations where the possibilities for substitution among the heterogeneous items can be expressed as a matrix. Henceforth, the term “requirements matrix” will refer to a matrix of rows and columns which expresses the possibilities for substitution among the heterogeneous goods, the seller(s) or the buyer(s). The same information could be equivalently expressed as a graph.
[0029] For example, one embodiment of the present invention has useful application in the allocation of capacity for a gas pipeline system. Let Types 1-4 denote four geographically-dispersed terminals where gas may enter the pipeline system. The party on whose behalf the auction is conducted may wish to purchase 100 units of entry rights in aggregate. However, it may be the case that: 40 of these units are required to be of Type 2, since 40 units of gas are produced at a field that is located in close geographic proximity to the terminal corresponding to Type 2; 35 of these units are required to be of Types 3 or 4, since 35 units of gas are produced at fields that are located in close geographic proximity to the terminals corresponding to Types 3 and 4; while the remaining 25 units can be of any Types 1-4, since 25 units of gas are brought in by ship and can be landed equally easily at any of these terminals. This situation is depicted by the requirements matrix in Table 1:
TABLE 1 Units required Type 1 Type 2 Type 3 Type 4 ( 0 0 25 40 0 25 0 35 25 0 35 25 )
[0030] A second embodiment of the invention treats a situation where there are three types of items (m=3)—Type 1, Type 2 and Type 3—being sold. The party on whose behalf the auction is conducted may wish to sell fixed quantities of these three individual types of items. However, it may still be the case that it is advantageous to sell them together, since bidders may find: that information revealed in the auction about one type of these items is relevant to the value of another type of these items; or that they are relatively more interested in one type of these items, or another, depending upon their relative prices. This situation is depicted by the requirements matrix in Table 2:
TABLE 2 Units required Type 1 Type 2 Type 3 ( 2000 0 0 0 2000 0 0 0 1000 )
[0031] One useful application of this second embodiment occurs in the context of selling Treasury or other securities. A government or central bank may wish to simultaneously auction 3-month, 6-month and 12-month Treasury securities. Let us denote these three types of Treasury securities as Type 1, Type 2 and Type 3, respectively. The requirements matrix of Table 2 would say that the government or central bank has 2000 units of 3-month Treasury securities, 2000 units of 6-month Treasury securities, and 1000 units of 12-month Treasury securities.
[0032] A third, and mathematically simpler, embodiment of the present invention treats the situation where two types of items (m=2)—Type 1 and Type 2—are being procured. The party on whose behalf the auction is conducted may wish to purchase four units in aggregate. However, it may be the case that three of these units are required to be of Type 1, while the fourth unit can either be of Type 1 or Type 2. This situation is depicted by the requirements matrix in Table 3:
TABLE 3 Units required Type 1 Type 2 ( 1 1 1 1 0 0 0 1 )
[0033] One useful application of this third embodiment of the invention may occur in the clearing or relocation of television stations. For example, to clear the communications spectrum currently occupied by UHF Channels 59-69 in a given regional market, it might be necessary to relocate three analog and one digital television stations to lower channels. Let Type 1 denote an analog television station and let Type 2 denote a digital television station. Suppose that an analog station in UHF Channels 59-69 must be relocated to a frequency allocated to analog stations below Channel 59, while a digital station in UHF Channels 59-69 may be relocated to a frequency allocated to either an analog or a digital station below Channel 59. Then the requirements matrix of Table 3 would accurately describe the possibilities for substitution. In particular, the party on whose behalf the auction is held would be satisfied by purchasing four items of Type 1 or by purchasing three items of Type 1 and one item of Type 2. Generally speaking, since this is a procurement auction, this party would prefer whichever of these purchases cost less money.
DEFINITIONS
[0034] The available quantity ({overscore (Q)} 1 , . . . , {overscore (Q)} m ) refers to the quantity of each type of item offered for sale in the auction, in the case of an auction to sell, and the quantity of each type of item offered to be procured in the auction, in the case of an auction to buy (i.e., a reverse auction). Optionally, the available quantity may be allowed to depend on the price, or otherwise be contingent on the progress of the auction.
[0035] The bidding state consists of the current bids {Q 1 i , . . . , Q m i } i=1 n of all the bidders, the available quantity, and the quantity vectors (if any) that have already been awarded to bidders. Optionally, bids may be permitted to be more complicated than merely a vector of quantities: for example, bids may be permitted to include prices or to be contingent on events, to contain “and” and “or” restrictions, and to include minimum acceptable quantities. Bids may also be permitted to specify arbitrary sets, or combinations of sets, of specifically-identified objects, as opposed to merely comprising quantities of types of objects.
[0036] The set of feasible assignments given the bidding state is the set of all possible allocations {x 1 i , . . . , x m i } i=1 n of the available quantity of the m types of items to the n bidders, subject to satisfying all the constraints on the assignment of the goods, the constraints on the bidding process and the constraints posed by the bidding state. The following conditions (i)-(iv) are exemplary of the requirements on {x 1 i , . . . , x m i } i=1 n to be a feasible assignment:
(i) x k i ≧0 for every k=1, . . . , m, and for every 1, . . . , n; (ii) Σ i=1 n x k i ={overscore (Q)} k ; (iii) {x 1 i , . . . , x m i } i=1 n is consistent with the requirements matrix or other constraints on the assignment of the items; (iv) {x 1 i , . . . , x m i } i=1 n is consistent with activity rules constraining the bidding process, given current bids {Q 1 i , . . . , Q m i } i=1 n (e.g., x k i ≦Q k i for every k=1, . . . , m, and for every i=1, . . . , n).
[0041] The winning set of bidder i is the set W i of all (x 1 i , . . . , x m i ) that are part of a feasible assignment (i.e., the set of feasible assignments for all bidders, projected onto bidder i).
[0042] We will write that a quantity vector (a 1 , . . . , a m )≧(b 1 , . . . , b m ), if a k ≧b k for every k=1, . . . , m, and if a k >b k for some k=1, . . . m.
[0043] A quantity vector (q 1 i , . . . , q m i ) is said to be minimal in the winning set of bidder i if (q 1 i , . . . , q m i ) ε W i but (r 1 i , . . . , r m i ) ∉ W i whenever (q 1 i , . . . , q m i )≧(r 1 i , . . . , r m i ).
[0044] A bidder i is said to have clinched a quantity vector (q 1 i , . . . , q m i ) if, given the available quantity, his opponents' bids and the various constraints on the auction, the bidder is mathematically guaranteed to win at least the quantity vector (q 1 i , . . . , q m i ). In the above notation, bidder i clinches a quantity vector (q 1 i , . . . , q m i ) if (q 1 i , . . . , q m i )≧0 and if (q 1 i , . . . , q m i ) is minimal in the winning set of bidder i.
[0045] The definition of clinching can be restated in simpler form in general set notation. Let Ω denote the set of available objects. An assignment is defined to be an n-tuple of subsets, {S i } i=1 n , where S i denotes the subset of objects assigned to bidder i. A feasible assignment is an n-tuple of subsets, {S i } i=1 n , with the properties that: {S i } i=1 i assigns every available object to exactly one bidder (i.e., the set union of {S i } i=1 i equals Ω, and the {S i } i=1 n are pairwise disjoint); {S i } i=1 n is consistent with the requirements matrix or other constraints on the assignment of the objects; and {S i } i=1 n is consistent with any activity rules constraining the bidding process, given the current bidding state. The winning set of bidder i is the set W i of all subsets of objects, S i , that are assigned to bidder i in some feasible assignment (i.e., the set of feasible assignments for all bidders, projected onto bidder i). A subset S i of objects is said to be minimal in the winning set of bidder i if S i ε W i , but R i ∉ W i whenever R i is a strict subset of S i (i.e., there is no strict subset of S i that is feasible for bidder i to win). Analogous to the previous paragraph, bidder i clinches a subset S i of objects if S i Ø (i.e., S i is a nonempty set of objects) and S i is minimal in the winning set of bidder i.
[0046] A second, almost equivalent way of describing clinching is that the quantity vector (q 1 i , . . . , q m i ) is clinched if it constitutes a maximal quantity vector that bidder i is guaranteed to win. The quantity vector (q 1 i , . . . , q m i ) is a maximal quantity vector that bidder i is guaranteed to win if: bidder i is guaranteed to win (q 1 i , . . . q m i ); but there does not exist any quantity vector (r 1 i , . . . , r m i )≧(q 1 i , . . . , q m i ) such that bidder i is guaranteed to win the quantity vector (r 1 i , . . . , r m i ).
[0047] A third, and apparently equivalent way of describing clinching is in terms of admissible fictitious bids. We will say that ({tilde over (Q)} 1 i , . . . , {tilde over (Q)} m i ) is an admissible fictitious bid if the following three conditions are all satisfied:
(i) 0≦{tilde over (Q)} k i ≦Q k i , for every k=1, . . . , m; (ii) {tilde over (Q)} k i >0, for some k=1, . . . , m; and (iii) {tilde over (Q)} i satisfies any extra requirements of the auction such as consisting entirely of integer numbers.
For any Bidder i and for any fictitious bid {tilde over (Q)} i under consideration, the computer determines an answer to the following question: “If Bidder i's actual bid (Q 1 i , . . . , Q m i ) were replaced by the admissible fictitious bid ({tilde over (Q)} 1 i , . . . , {tilde over (Q)} m i ), and if the other bidders continued to use their actual bids, would the auction conclude?” If the answer to this question is affirmative, then Bidder i can also be viewed as having guaranteed winning the units (Q 1 i -{tilde over (Q)} 1 i , . . . , Q m i -{tilde over (Q)} m i ). The auction procedure takes note of this determination in assigning objects.
[0051] The principles underlying “clinching”—and the algorithm determining “clinching”—are easiest illustrated with some examples:
[0052] EXAMPLE 1
[0053] The requirements matrix for units of each of the two types is given by Table 3. The auction is conducted as a procurement auction, and four bidders (superscripted by i=1,2,3,4) participate. At every price p, each bidder i indicates a pair (Q 1 i , Q 2 i ), which gives the number of units of Type 1 and the number of units of Type 2, respectively, that he is willing to sell at price p. Suppose that, for a given price p, the following Table 4A shows the quantities that the bidders have indicated:
TABLE 4A Q 1 i Q 2 i Bidder 1 2 0 Bidder 2 1 0 Bidder 3 0 1 Bidder 4 1 0
To begin, observe that the auction has not yet concluded, and that the auctioneer may continue by naming a new, lower price. The reason for this observation is that the party on whose behalf the auction is being conducted only wishes to purchase either 3 units of Type 1 and 1 unit of Type 2, or 4 units of Type 1 (see Table 3), whereas Bidders 1 - 4 are in aggregate offering 4 units of Type 1 and 1 unit of Type 2 (i.e., strictly more than is required). However, suppose we take any Bidder i (i=1,2,3,4) and consider the following question: “Are there any types of any units that Bidder i is already guaranteed to have won (given other bidders' bids)?” If the answer to this question is affirmative, then Bidder i will be said to have clinched such units.
[0054] In Example 1, let us begin by considering Bidder 1 . Since Bidder 1 is only bidding on units of Type 1, Bidder 1 can only clinch units of Type 1. Observe that any feasible way of satisfying the requirements matrix includes Bidder 1 winning on at least 1 unit of Type 1. (This follows from the fact that, in the requirements matrix of Table 3, at least 3 units of Type 1 are required, but Bidders 2 - 4 are collectively bidding only 2 units of Type 1.) Thus, Bidder 1 has clinched one unit of Type 1. One way that the auctioneer may act on this determination is to assign one unit of Type 1 to Bidder 1 at the price associated with the first time that Bidder 1 was determined to have clinched one unit of Type 1.
[0055] At the same time, observe that one feasible way of satisfying the requirements matrix is using the following bids: (Q 1 1 , Q 2 1 )=(1,0); (Q 1 2 , Q 2 2 )=(1,0); (Q 1 3 , Q 2 3 )=(0,1); and (Q 1 4 , Q 2 4 )=(1,0). Since this feasible way of satisfying the requirements matrix has Bidder 1 winning only one unit of Type 1, we conclude that Bidder 1 has not clinched two units of Type 1.
[0056] To put things slightly differently, but equivalently, the winning set for Bidder 1 in Example 1 is W 1 ={(1,0), (2,0)}. There is no feasible assignment in which Bidder 1 is assigned (0,0). Thus, (1,0) is minimal in the winning set, W 1 , of Bidder 1 , and so Bidder 1 clinches the quantity vector (1,0). Put differently, if Bidder 1 's actual bid of (2,0) were replaced by the admissible fictitious bid (1,0), then the auction would end; thus, Bidder 1 clinches the difference (2,0)−(1,0) =(1,0).
[0057] Also at the same time, observe that Bidders 2 - 4 have not yet clinched any units. The requirements matrix can be satisfied using the bids: (Q 1 1 , Q 2 1 )=(2,0); (Q 1 2 , Q 2 2 )=(0,0); (Q 1 3 , Q 2 3 )=(0,1); and (Q 1 4 , Q 2 4 )=(1,0). This does not involve Bidder 2 winning anything at all. The requirements matrix can also be satisfied using the bids: (Q 1 1 , Q 2 1 )=(2,0); (Q 1 2 , Q 2 2 )=(1,0); (Q 1 3 , Q 2 3 )=(0,0); and (Q 1 4 , Q 2 4 )=(1,0). This does not involve Bidder 3 winning anything at all. Finally, the requirements matrix can also be satisfied using the bids: (Q 1 1 , Q 2 1 )=(2,0); (Q 1 2 , Q 2 2 )=(1,0); (Q 1 3 , Q 2 3 )=(0,1); and (Q 1 4 , Q 2 4 )=(0,0). This does not involve Bidder 4 winning anything at all.
EXAMPLE 2
[0058] The requirements matrix for units of each of the two types is again given by Table 3. The auction is conducted as a procurement auction, and four bidders (superscripted by i=1,2,3,4) participate. At every price p, each bidder i indicates a pair (Q 1 i , Q 2 i ), which gives the number of units of Type 1 and the number of units of Type 2, respectively, that he is willing to sell at price p. Suppose that, for a given price p, the following Table 4B shows the quantities that the bidders have indicated:
TABLE 4B Q 1 i Q 2 i Bidder 1 1 1 Bidder 2 1 0 Bidder 3 0 1 Bidder 4 1 0
To begin, observe that the auction has not yet concluded, and that the auctioneer may continue by naming a new, lower price. The reason for this observation is that the party on whose behalf the auction is being conducted only wishes to purchase either 3 units of Type 1 and 1 unit of Type 2, or 4 units of Type 1 (see Table 3), whereas Bidders 1 - 4 are in aggregate offering 3 units of Type 1 and 2 units of Type 2 (i.e., strictly more than is required).
[0059] In Example 2, let us begin by considering Bidder 1 . Since Bidder 1 is bidding on units of Type 1 and Type 2, Bidder 1 can in principle clinch units of Type 1 or Type 2. Observe that any feasible way of satisfying the requirements matrix includes Bidder 1 winning 1 unit of Type 1. (This follows from the fact that, in the requirements matrix of Table 3, at least 3 units of Type 1 are required, but Bidders 2 - 4 are collectively bidding only 2 units of Type 1.) Thus, Bidder 1 has clinched one unit of Type 1 . One way that the auctioneer may act on this determination is to assign one unit of Type 1 to Bidder 1 at the price associated with the first time that Bidder 1 was determined to have clinched one unit of Type 1.
[0060] Bidders 2 and 4 have also clinched one unit of Type 1. (For Bidder 2 , this follows from the fact that, in the requirements matrix of Table 3, at least 3 units of Type 1 are required, but Bidders 1 , 3 and 4 are collectively bidding only 2 units of Type 1.) (For Bidder 4 , this follows from the fact that, in the requirements matrix of Table 3, at least 3 units of Type 1 are required, but Bidders 1 , 2 and 3 are collectively bidding only 2 units of Type 1.) One way that the auctioneer may act on this determination is to assign one unit of Type 1 to Bidder 2 at the price associated with the first time that Bidder 2 was determined to have clinched one unit of Type 1, and similarly for Bidder 4 .
[0061] At the same time, observe that Bidder 1 has not clinched one unit of Type 2. This is because one feasible way of satisfying the requirements matrix is using the following bids: (Q 1 1 , Q 2 1 )=(1,0); (Q 1 2 , Q 2 2 )=(1,0); (Q 1 3 , Q 2 3 )=(0,1); and (Q 1 4 , Q 2 4 )=(1,0). Since this feasible way of satisfying the requirements matrix has Bidder 1 winning zero units of Type 2, we conclude that Bidder 1 has not clinched any units of Type 2.
[0062] Also at the same time, observe that Bidder 3 has not yet clinched any units. The requirements matrix can be satisfied using the bids: (Q 1 1 , Q 2 1 )=(1,1); (Q 1 2 , Q 2 2 )=(1,0); (Q 1 3 , Q 2 3 )=(0,0); and (Q 1 4 , Q 2 4 )=(1,0). This does not involve Bidder 3 winning anything at all.
EXAMPLE 3
[0063] Let the requirements matrix for units of each of three types now be given by Table 2. The auction is conducted as a selling auction, and four bidders (superscripted by i=1,2,3,4) participate. At every price vector (p 1 ,p 2 ,p 3 ), each bidder i indicates a vector (Q 1 i , Q 2 i , Q 3 i ), which gives the number of units of Type 1 that he is willing to purchase at price p 1 , the number of units of Type 2 that he is willing to purchase at price p 2 , and the number of units of Type 3 that he is willing to purchase at price p 3 . Suppose that, for a given price vector (p 1 , p 2 , p 3 ), the following Table 5 shows the quantities that the bidders have indicated:
TABLE 5 Q 1 i Q 2 i Q 3 i Bidder 1 1000 0 500 Bidder 2 500 1000 100 Bidder 3 500 1000 200 Bidder 4 500 0 600
We might also suppose that, as the auction continues, each bidder is only allowed to bid the same quantity or lower on each type of item.
[0064] To begin, observe that the auction has not yet concluded on Type 1 and Type 3, and that the auctioneer may continue by naming a new, higher prices p 1 and p 3 . The reason for this observation is that the party on whose behalf the auction is being conducted only wishes to sell 2000 units of Type 1, whereas Bidders 1 - 4 are in aggregate demanding 2500 units of Type 1 (i.e., strictly more than is required), and the party on whose behalf the auction is being conducted only wishes to sell 1000 units of Type 3, whereas Bidders 1 - 4 are in aggregate demanding 1400 units of Type 3 (i.e., strictly more than is required).
[0065] In Example 3, since the requirements matrix is a diagonal matrix, one may choose to treat the three types of units separately. Let us begin by considering Type 1. In considering Type 1, let us begin with Bidder 1 . Observe that any feasible way of satisfying the requirements matrix includes Bidder 1 winning (at least) 500 units of Type 1. (This follows from the fact that, in the requirements matrix of Table 5, there are 2000 units of Type 1 required, but Bidders 2 - 4 are collectively bidding only 1500 units of Type 1.) Thus, Bidder 1 has clinched 500 units of Type 1. One way that the auctioneer may act on this determination is to assign units of Type 1 to Bidder 1 at the price associated with the first time that Bidder 1 was determined to have clinched the given unit of Type 1.
[0066] At the same time, observe that Bidders 2 - 4 have not yet clinched any units of Type 1. The requirements for Type 1 can be satisfied using the quantities: Q 1 1 =1000; Q 1 2 =0; Q 1 3 =500; and Q 1 4 =500. This does not involve Bidder 2 winning any of Type 1 at all. The requirements for Type 1 can also be satisfied using the quantities: Q 1 1 =1000; Q 1 2 =500; Q 1 3 =0; and Q 1 4 =500. This does not involve Bidder 3 winning any of Type 1 at all. The requirements for Type 1 can also be satisfied using the quantities: Q 1 1 =1000; Q 1 2 =500; Q 1 3 =500; and Q 1 4 =0. This does not involve Bidder 4 winning any of Type 1 at all.
[0067] Turning to Type 2, observe that the auction of Type 2 items has effectively concluded. In clinching terms, Bidders 2 and 3 have each clinched 1000 units of Type 2, and their combined clinches equals the entire requirements of 2000. This follows from the fact that the only feasible way in which the requirements for Type 2 can be satisfied is using the quantities: Q 2 1 =0; Q 2 2 =1000; Q 2 3 =1000; and Q 2 4 =0.
[0068] Turning to Type 3, let us begin by considering Bidder 1 . Observe that any feasible way of satisfying the requirements matrix includes Bidder 1 winning (at least) 100 units of Type 3. (This follows from the fact that, in the requirements matrix of Table 2, there are 1000 units of Type 3 required, but Bidders 2 - 4 are collectively bidding only 900 units of Type 3.) Thus, Bidder 1 has clinched 100 units of Type 3. One way that the auctioneer may act on this determination is to assign units of Type 3 to Bidder 1 at the price associated with the first time that Bidder 1 was determined to have clinched the given unit of Type 3. Let us next consider Bidder 4 . Observe that any feasible way of satisfying the requirements matrix includes Bidder 4 winning (at least) 200 units of Type 3. (This follows from the fact that, in the requirements matrix of Table 2, there are 1000 units of Type 3 required, but Bidders 1 - 3 are collectively bidding only 800 units of Type 3.) Thus, Bidder 4 has clinched 200 units of Type 3. One way that the auctioneer may act on this determination is to assign units of Type 3 to Bidder 4 at the price associated with the first time that Bidder 4 was determined to have clinched the given unit of Type 3.
[0069] At the same time, observe that Bidders 2 and 3 have not clinched any units of Type 3. This is because one feasible way in which the requirements for Type 3 can be satisfied is using the quantities: Q 3 1 =400; Q 3 2 =0; Q 3 3 =0; and Q 3 4 =600. This does not involve Bidder 2 or Bidder 3 winning any of Type 3 at all.
[0070] FIG. 3 is a flow diagram of an auction process in accordance with one embodiment of the present invention. The process starts with step 202 , in which memory locations at the computer are initialized. In step 202 , the appropriate memory locations are initialized with information such as the number of types of objects for auction, the quantity of each type of object for auction, and the initial price vector. In step 204 , the computer outputs auction information, including the current price vector (P 1 , . . . , P m ). In step 206 , the computer receives bids (Q 1 i , . . . , Q m i ) from bidders. In step 208 , the computer closes the bidding for the current round and processes bids. This process is shown in more detail in FIG. 5 . In step 210 , the computer determines whether: (a) there exist zero feasible assignments of the available quantity; (b) there exists one feasible assignment of the available quantity; or (c) there exist two or more feasible assignments of the available quantity. If, at step 210 , the computer determines that (c) there exist two or more feasible assignments of the available quantity, then the process goes to step 216 in which the computer determines whether any units have been clinched by any bidders and, if so, assigns clinched units to determined bidders at current prices. This process is shown in more detail in FIG. 4 a, and one preferred embodiment of this process is shown in more detail in FIG. 4 b. The process then goes to step 218 in which the computer revises the current price vector (P 1 , . . . , P m ) and generates the bidding history and any auction announcements and messages. One exemplary rule for revising the price is that, for every k=1, . . . , m, the price P k of objects of type k is raised by c[(Σ i=1 n Q k i,t )−{overscore (Q)} k t ], where c is a positive constant (i.e., the price for each type is increased in direct proportion to the excess demand for that type). The process then loops to step 204 .
[0071] If, at step 210 , the computer determines that (a) there exist zero feasible assignments of the available quantity, then the process goes to step 212 in which the computer assigns units in accordance with a rationing rule. One exemplary rationing rule is for the computer to honor the various bidders' attempts to decrease their bids by time priority (i.e., in the order that the bids were submitted) so long as a feasible assignment continues to exist. A second exemplary rationing rule is for the computer to increase each bidder's quantity bid in constant proportion to the bidder's most recent attempted reduction, Q k i,t-1 −Q k i,t , until one assignment becomes feasible. If, at step 210 , the computer determines that (b) there exists one feasible assignment of the available quantity, then the process goes to step 214 in which the computer assigns units in accordance with the one feasible assignment. After steps 212 or 214 , the auction is deemed to have ended, and so the process ends.
[0072] FIG. 4 a is a flow diagram of a subprocess of step 216 . It begins with step 216 a - 1 , in which a bidder i which has not yet been considered is selected. In step 216 a - 2 , for the bidder i currently being considered, the computer determines whether there exists a quantity vector (q 1 i , . . . , q m i )≧0 that bidder i is guaranteed to win. If there does not exist such a quantity vector (q 1 i , . . . , q m i )≧0, the process proceeds directly to step 216 a - 7 . If there does exist such a quantity vector (q 1 i , . . . , q m i )≧0, the process continues with step 216 a - 3 , in which the computer determines a maximal quantity vector (q 1 i , . . . , q m i )≧0 that bidder i is guaranteed to win. The quantity vector (q 1 i , . . . , q m i ) is said to be a maximal quantity vector that bidder i is guaranteed to win (or a maximal guaranteed quantity vector) if: bidder i is guaranteed to win (q 1 i , . . . , q m i ); but there does not exist any quantity vector (r 1 i , . . . , r m i )≧(q 1 i , . . . , q m i ) such that bidder i is guaranteed to win the quantity vector (r 1 i , . . . , r m i ). The process then continues with step 216 a - 4 , in which the computer determines whether the maximal guaranteed quantity vector (q 1 i , . . . , q m i )≧0 generated in step 216 a - 3 is unique. If it is unique, the process proceeds directly to step 216 a - 6 . If it is not unique, the process continues with step 216 a - 5 , in which the computer determines a most-preferred maximal quantity vector (q 1 i , . . . , q m i ) that bidder i is guaranteed to win. One exemplary way of selecting a most-preferred maximal guaranteed quantity vector that bidder i is guaranteed to win is to calculate a maximal guaranteed quantity vector (q 1 i , . . . , q m i ) such that the difference between the expected final price vector and the current price vector, multiplied by (q 1 i , . . . , q m i ) as a dot product, is minimized. In step 216 a - 6 , the computer assigns the determined quantity vector, (q 1 i , . . . , q m i ), to bidder i at the current price vector (P 1 , . . . , P m ). In step 216 a - 7 , the computer determines whether all bidders have been considered. If not, the process loops back to step 216 a - 1 . If all bidders have been considered, the process goes to step 218 of FIG. 3 .
[0073] FIG. 4 b is a flow diagram of one preferred embodiment of the process shown in FIG. 4 a. It is also a flow diagram of a subprocess of step 216 . It begins with step 216 b - 1 , in which the computer selects a bidder i which has not yet been considered. In step 216 b - 2 , the computer selects a type k which has not yet been considered. In step 216 b - 3 , the computer sums the quantities demanded of the type k objects by all the bidders except bidder i, and compares this sum with the quantity remaining unassigned of type k objects. If the computer determines that the quantity remaining unassigned of type k objects is not strictly greater than the sum of the quantities demanded of the type k objects by all the bidders except bidder i, then the process proceeds directly to step 216 b - 5 . If the computer determines that the quantity remaining unassigned of type k objects is strictly greater than the sum of the quantities demanded of the type k objects by all the bidders except bidder i, then the process continues with step 216 b - 4 . In step 216 b - 4 , the computer assigns the quantity {overscore (Q)} k −Σ j≠i Q k i or the quantity Q k i —whichever of the two quantities is smaller—of objects of type k to bidder i. The process then proceeds with step 216 b - 5 , in which the computer determines whether all types have been considered for bidder i. If not, the process loops back to step 216 b - 2 . If all types have been considered for bidder i, the process continues with step 216 b - 6 , in which the computer determines whether all bidders have been considered. If not, the process loops back to step 216 b - 1 . If all bidders have been considered, the process goes to step 218 of FIG. 3 .
[0074] FIG. 5 is a flow diagram of a subprocess of step 208 . It begins with step 208 - 1 , in which the computer selects a bidder which has submitted a bid but which has not yet been considered. This bidder is denoted bidder i. One exemplary way of selecting which bidder to consider is to select the earliest-time-stamped bid which has not yet been considered. In step 208 - 2 , the computer recalls from memory the most recent previously-processed bid by bidder i, the bidder currently being considered. The most recent previously-processed bid is denoted (Q 1 i,t-1 , . . . , Q m i,t-1 ). In step 208 - 3 , the computer determines whether bidder i's current bid satisfies an eligibility rule, for example: Q k i,t ≦Q k i,t-1 . If bidder i's current bid satisfies the eligibility rule, then the process skips to step 208 - 5 . If bidder i's current bid does not satisfy the eligibility rule, the process continues with step 208 - 4 , in which the computer adjusts bidder i's current bid so as to satisfy the eligibility rule. One exemplary way of doing this is to insert bidder i's most recent previously-processed bid, (Q 1 i,t-1 , . . . , Q m i,t-1 ), as bidder i's current bid. In step 208 - 5 , the computer determines whether bidder i's current bid satisfies the additional constraints: Σ j=1 n Q k j ≧{overscore (Q)} k , for all types k=1, . . . , m. If bidder i's current bid satisfies these additional constraints, then the process skips to step 208 - 7 . If bidder i's current bid does not satisfy these additional constraints, the process continues with step 208 - 6 , in which the computer adjusts bidder i's bid so as to satisfy the additional constraints. One exemplary way of doing this is to insert bidder i's most recent previously-processed bid, (Q 1 i,t-1 , . . . , Q m i,t-1 ), as bidder i's current bid. A second exemplary way of doing this is to substitute Q k i with {overscore (Q)} k −Σ j≠i Q k j as bidder i's quantity for type k, for every k=1, . . . , m violating the additional constraint. In step 208 - 7 , the computer determines whether all bidders who have submitted bids have yet been considered. If not, the process loops back to step 208 - 1 . If all bidders have been considered, the process goes to step 210 of FIG. 3 .
[0075] Another embodiment of the inventive system is described by a slightly different flow diagram, FIG. 6 . The difference between FIG. 3 and FIG. 6 is that—in FIG. 6 —the step 316 is deferred until the end of the auction. In that event, the auctioneer is allowed to wait until the conclusion of the auction to determine which objects were assigned at which prices in the course of the auction.
[0076] FIG. 6 is thus a flow diagram of an auction process in accordance with another embodiment of the present invention. The process starts with step 302 , in which memory locations at the computer are initialized. In step 302 , the appropriate memory locations are initialized with information such as the number of types of objects for auction, the quantity of each type of object for auction, and the initial price vector. In step 304 , the computer outputs auction information, including the current price vector (P 1 , . . . , P m ). In step 306 , the computer receives bids (Q 1 i , . . . , Q m i ) from bidders. In step 308 , the computer closes the bidding for the current round and processes bids. This process is shown in more detail in FIG. 5 (but with “From Step 206 ” replaced by “From Step 306 ”, and with “To Step 210 ” replaced by “To Step 310 ”, etc.). In step 310 , the computer determines whether: (a) there exist zero feasible assignments of the available quantity; (b) there exists one feasible assignment of the available quantity; or (c) there exist two or more feasible assignments of the available quantity. If, at step 310 , the computer determines that (c) there exist two or more feasible assignments of the available quantity, then the process goes to step 318 in which the computer revises the current price vector (P 1 , . . . , P m ) and generates the bidding history and any auction announcements and messages. One exemplary rule for revising the price is that, for every k=1, . . . , m, the price P k of objects of type k is raised by c[(Σ i=1 n Q k i,t )−{overscore (Q)} k t ], where c is a positive constant (i.e., the price for each type is increased in direct proportion to the excess demand for that type). The process then loops to step 304 .
[0077] If, at step 310 , the computer determines that (a) there exist zero feasible assignments of the available quantity, then the process goes to step 312 in which the computer assigns units in accordance with a rationing rule. One exemplary rationing rule is for the computer to honor the various bidders' attempts to decrease their bids by time priority (i.e., in the order that the bids were submitted) so long as a feasible assignment continues to exist. A second exemplary rationing rule is for the computer to increase each bidder's quantity bid in constant proportion to the bidder's most recent attempted reduction, Q k i,t-1 −Q k i,t , until one assignment becomes feasible. If, at step 310 , the computer determines that (b) there exists one feasible assignment of the available quantity, then the process goes to step 314 in which the computer assigns units in accordance with the one feasible assignment. After steps 312 or 314 , the process goes to step 316 in which the computer determines bidders' payments for units assigned, retroactively, in accordance with current prices at the time the units were clinched. If, at every time that units were clinched, the maximal quantity vector (q 1hu i , . . . , q m i ) that bidder i was guaranteed to win was unique, then the determination of payments is straightforward. For the case where the sequence of maximal guaranteed quantity vectors (q 1 i , . . . , q m i ) for bidder i was not unique, one exemplary way for the computer to determines bidders' payments is to determine the sequence of maximal guaranteed quantity vectors consistent with the ultimate assignment of units that maximizes bidder i's payment. After step 316 , the auction is deemed to have ended, and so the process ends.
[0078] Another embodiment of the inventive system is described by the same flow diagrams—except with step 216 or step 316 (and hence FIGS. 4 a and 4 b ) deleted. In that event, the auction still proceeds with multiple ascending clocks, but now objects are not assigned in intermediate rounds, and so every object of a given type is assigned at the same price.
Further Embodiments with Interactions Among Different Types of Units
[0079] The embodiments of the present invention that have thus far been discussed in this document have been premised, in their logic, on an activity rule which considered each type of unit separately. Each bidder was constrained to bid a quantity on each type of unit that is no greater than any of his earlier quantities bid on that same type of unit. In notation, Q k i,t ≦Q k i,t-1 , for every k=1, . . . , m.
[0080] In many applications, it may be advantageous to instead use an activity rule which allows interactions among different types of units. One of the simplest examples is an activity rule for a bidder under which the aggregate quantity bid for all types of units is constrained to be no greater than any of his earlier aggregate quantities bid for all types of units. In notation, Σ k=1 m Q k i,t ≦Σ k=1 m Q k i,t-1 .
[0081] Observe that the latter activity rule is a looser constraint on bidders than the former activity rule. For example, in Example 3 (see also Tables 2 and 5), a bid of (500, 0, 600) may be followed by a bid of (600, 300, 100) under the latter activity rule, but not under the former activity rule. Since more possible future bids exist under the latter activity rule, smaller quantities are determined to have clinched at a given bidding state when analyzed under the latter activity rule.
[0082] Activity rules that allow interactions among different types of units may be particularly advantageous in applications where substitution among the different types of units are most relevant to bidders. For example, in the application to allocation of capacity for a gas pipeline system, a bidder may be bringing in his gas by ship, and may be able to equally easily use any of four terminals. In that event, all he may really care about is his aggregate quantity summed over the four terminals (adjusted for minor cost differences among the terminals). In the application to selling Treasury securities, a bidder may be looking for a safe short-term investment, and may be able to equally easily use 3-month, 6-month or 12-month Treasury securities. Let us denote these three types of Treasury securities as Type 1, Type 2 and Type 3, respectively. In that event, all he may really care about is his aggregate quantity summed over the three times to maturity (adjusted for price differences on the yield curve).
[0083] FIG. 7 is a flow diagram of an auction process in accordance with one embodiment of the present invention. The process starts with step 102 , in which memory locations are initialized. In step 102 , the appropriate memory locations are initialized with information such as the number of types of objects for auction, the quantity of each type of object for auction, and the initial price vector. In step 104 , the bidding information processor transmits auction information, including the starting price vector (P 1 , . . . , P m ), and transmits it to bid entry terminals. In step 106 , bid entry terminals receive auction information from the bidding information processor and display it to bidders. In step 108 , bid entry terminals receive bids (Q 1 i , . . . , Q m i ) from bidders and transmit them to the bidding information processor. In step 110 , the bidding information processor receives the bids transmitted from bid entry terminals and transmits confirmation messages. In step 112 , the bidding information processor closes the bidding for the current round and processes bids received from bid entry terminals. This process is shown in more detail in FIG. 9 . In step 114 , the bidding information processor assigns objects, if any, at the current prices. This process is shown in more detail in FIGS. 8 a, 8 b and 8 c. In step 116 , the bidding information processor determines if any objects remain unassigned. If so, the process goes to step 118 in which the bidding information processor increments the current price vector and generates the bidding history and any auction announcements and messages. One exemplary rule for incrementing the price is that, for every k=1, . . . , m, the price P k of objects of type k is raised by c[(Σ i=1 n Q k i,t )−{overscore (Q)} k t ], where c is a positive constant (i.e., the price for each type is increased in direct proportion to the excess demand for that type). The process then loops to step 104 . If no objects remain unassigned, then the process ends.
[0084] FIG. 8 a is a flow diagram of a subprocess of step 114 . It begins with step 114 - 1 , in which the bidding information processor sums the quantities demanded by all the bidders and for all the types of objects; also sums the quantities remaining unassigned of all the types of objects; and computes the difference between the two sums. In step 114 - 2 , the bidding information processor determines whether the difference between these two sums is (strictly) greater than zero. If the difference between the two sums is (strictly) greater than zero, the process continues with step 114 - 3 , in which the bidding information processor considers each bidder separately and determines an assignment of objects at the current prices. This step is shown in more detail in FIG. 8 b. The process then goes to step 116 of FIG. 7 . If the difference between the two sums is not (strictly) greater than zero, the process continues with step 114 - 4 , in which each bidder is assigned the quantity bid for each type of object at the current price, and since no objects remain unassigned, the auction ends after proceeding to step 116 of FIG. 7 .
[0085] FIG. 8 b is a flow diagram of a subprocess of step 114 - 3 . It begins with step 114 - 3 - 1 , in which a bidder which has not yet been considered is selected. In step 114 - 3 - 2 , for the bidder currently being considered, the bidding information processor sums the quantities remaining unassigned of all the types of objects; also it sums the quantities demanded by all the bidders other than the current bidder and for all the types of objects; and it computes the difference between the two sums. The difference is denoted {circumflex over (Q)} i . In step 114 - 3 - 3 , the bidding information processor determines whether {circumflex over (Q)} i is (strictly) greater than zero. If {circumflex over (Q)} i is not (strictly) greater than zero, no objects are assigned to the current bidder, and the process proceeds directly to step 114 - 3 - 6 . If {circumflex over (Q)} i is (strictly) greater than zero, the process continues with step 114 - 3 - 4 , in which the bidding information processor considers each type of object separately and determines an assignment of objects at the current prices. This step is shown in more detail in FIG. 8 c. In step 114 - 3 - 5 , the bidding information processor subtracts the assigned quantities from the bids of the current bidder and from the quantities for auction. In step 114 - 3 - 6 , it is determined whether all bidders have been considered. If not, the process loops back to step 114 - 3 - 1 . If all bidders have been considered, the process goes to step 116 of FIG. 7 .
[0086] FIG. 8 c is a flow diagram of a subprocess of step 114 - 3 - 4 . It begins with step 114 - 3 - 4 - 1 , in which for every type k=1, . . . , m of object, the bidding information processor sums the quantity demanded of type k by all the bidders other than the current bidder, and subtracts this from the quantity remaining unassigned of type k. The difference is denoted {circumflex over (Q)} k i . In step 114 - 3 - 4 - 2 , the bidding information processor determines whether the sum of the {circumflex over (Q)} k i , summed over all types k=1, . . . , m of objects, equals {circumflex over (Q)} i . If the sum of the {circumflex over (Q)} k i equals {circumflex over (Q)} i , then the process continues with step 114 - 3 - 4 - 3 . In step 114 - 3 - 4 - 3 , ({circumflex over (Q)} 1 i , . . . , {circumflex over (Q)} m i ) is determined to be the assignment to bidder i, and the process goes to step 114 - 3 - 5 of FIG. 8 b. If the sum of the {circumflex over (Q)} k i does not equal {circumflex over (Q)} i , then the process continues with step 114 - 3 - 4 - 4 . In step 114 - 3 - 4 - 4 , the bidding information processor determines the most-preferred assignment (Q 1 i* , . . . , Q m i* ) which satisfies the following constraints: 0≦Q k i* ≦{circumflex over (Q)} k i for every type k=1, . . . , m; and Σ k=1 m Q k i* ={circumflex over (Q)} i . One exemplary way of selecting the most-preferred assignment is to select the (Q 1 i* , . . . , Q m i* ) consistent with the constraints such that the difference between the expected final price vector and the current price vector, multiplied by (Q 1 i* , . . . , Q m i* ) as a dot product, is minimized. The determined (Q 1 i* , . . . , Q m i* ) is deemed to be the assignment to bidder i, and the process goes to step 114 - 3 - 5 of FIG. 8 b.
[0087] FIG. 9 is a flow diagram of a subprocess of step 112 . It begins with step 112 - 1 , in which the bidding information processor considers a bidder who has submitted a bid which has not yet been considered. This bidder is denoted bidder i. One exemplary way of selecting which bidder to consider is to select the earliest-time-stamped bid which has not yet been considered. In step 112 - 2 , the bidding information processor recalls from memory the most recent previously-processed bid by bidder i, the bidder currently being considered. The previously-processed bid is denoted (Q 1 i,t-1 , . . . , Q m i,t-1 ). In step 112 - 3 , the bidding information processor determines whether bidder i's current bid satisfies the eligibility rule: Σ k=1 m Q k i,t ≦Σ k=1 m Q k i,t-1 . If bidder i's current bid satisfies the eligibility rule, then the process skips to step 112 - 5 . If bidder i's current bid does not satisfy the eligibility rule, the process continues with step 112 - 4 , in which the bidding information processor adjusts bidder i's bid so as to satisfy the eligibility rule. One exemplary way of doing this is to insert bidder i's most recent previously-processed bid, (Q 1 it-1 , . . . , Q m i,t-1 ), as bidder i's current bid. In step 112 - 5 , the bidding information processor determines whether bidder i's current bid satisfies the additional constraints: Σ j=1 n Q k j ≧{overscore (Q)} k , for all types k=1, . . . , m. If bidder i's current bid satisfies these additional constraints, then the process skips to step 112 - 7 . If bidder i's current bid does not satisfy these additional constraints, the process continues with step 112 - 6 , in which the bidding information processor adjusts bidder i's bid so as to satisfy the additional constraints. One exemplary way of doing this is to insert bidder i's most recent previously-processed bid, (Q 1 i,t-1 , . . . , Q m i,t-1 ), as bidder i's current bid. A second exemplary way of doing this is to substitute Q k i with {overscore (Q)} k −Σ j≠1 Q k j as bidder i's quantity for type k, for every k=1, . . . , m violating the additional constraint, provided that this substitution does not lead the eligibility rule to be violated. In step 112 - 7 , the bidding information processor determines whether all bidders who have submitted bids have yet been considered. If not, the process loops back to step 112 - 1 . If all bidders have been considered, the process goes to step 114 of FIG. 7 .
[0088] Another embodiment of the inventive system is described by the same flow diagrams—except with Step 114 - 3 - 4 - 4 deferred until the end of the auction. In that event, the auctioneer is allowed to wait until the conclusion of the auction to determine which objects were assigned at which prices in the course of the auction.
[0089] Another embodiment of the inventive system is described by the same flow diagrams—except with Step 114 - 3 (and hence FIGS. 8 b and 8 c ) deleted. In that event, the auction still proceeds with multiple ascending clocks, but now objects are not assigned in intermediate rounds, and so every object of a given type is assigned at the same price.
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A method and apparatus allow the computer based implementation of an auction of heterogeneous types of items wherein one or more types of the items may include plural items. At any point in the bidding process, the set of feasible assignments of the items, given the bidding state is the set of all possible allocations of the available quantity of the types of items to the bidders, subject to satisfying all the constraints on the assignment of the goods, the constraints on the bidding process and the constraints posed by the bidding state. Depending on the particulars of the bids, there may be one or more items (of one or more types) which are only included in the bid of a single bidder. The bidding is constrained such that once an item is uniquely spoken for, that bidder is guaranteed to receive the item. The item is said to be desired by only one bidder and such item is assigned to that bidder at the time. The auction continues until all items are assigned.
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BACKGROUND OF THE INVENTION
In an open-end spinning machine, the feed roller is rotated at a slow speed during the spinning operation. Thus, at the time of stopping the spinning operation, the feed roller may be stopped speedily by switching off the drive source. However, the combing roller is rotated during the spinning at a speed higher than 8,000 r.p.m. and thus it keeps on rotating for some time after the driving source is switched off. After the rotation of the feed roller is terminated, a certain amount of sliver is left on the surface of the feed roller. Since the combing roller is rotated by inertia, the sliver is fed little by little into the spinning rotor, as it is subjected to the combing action. The fiber thus supplied into the rotor is spun by the inertia rotation of the rotor into a long tennuous yarn which is connected integrally to the end of the spun yarn, as shown in FIG. 1. When the terminal yarn portion of such shape is fed into the rotor as an end yarn at the next spinning operation, it may not be entangled with the sliver at all or at least the yarn terminal portion will not be united evenly with the sliver.
BRIEF SUMMARY OF THE INVENTION
The present invention resides essentially in a method and an apparatus according to which the terminal portion of the spun yarn of the preceding open-end spinning operation may be used as a piecing-up end yarn at the restart of the spinning. The present invention is applied most effectively to a spinning system including a number of single spinning units wherein the yarn piecing up and winding operation is effected in unison at the respective spinning units after transient interruption of the spinning operation for maintenance and so forth. The present invention may also be applied to a spinning system where the cessation of spinning, the subsequent yarn piecing up operation and the restart of winding are effected separately at the respective spinning units.
It is an object of the present invention to realize a terminal portion of the spun yarn of the preceding spinning in such a way that said terminal portion may be used conveniently as an end yarn to be successfully pieced up to the fresh sliver. For this purpose, a suitable twist must be inserted in the end yarn. According to the present invention, the terminal portion of the spun yarn is taken up from the rotor at variable yarn speed in proportion to the rotor speed to maintain the normal spinning condition. Since the rotor is disconnected from the drive source upon issuance of an instruction signal for stopping the spinning, the rotor is rotated for some time by inertia, so that the twist may be inserted as desired to said terminal portion. By taking up the terminal portion at a speed compatible with the prevailing spinning speed, said portion may be fashioned as a continuous and integral part of the spun yarn without any sudden changes in the status of the yarn, such as number of twists per unit length. Thus, the spun yarn and the fresh sliver are pieced up to each other uniformly upon restarting the spinning operation. In addition, the combing roller of each spinning unit may be stopped suddenly by positively braking the combing roller upon cessation of the spinning, so as to prevent the useless supply of the fiber to the rotor which may result in a long and tenuous yarn end portion. Thus the yarn end portion highly convenient for the piecing up operation may be obtained, as shown schematically in FIG. 2.
Another object of the present invention is to get the yarn end portion introduced in an optimum state into the rotor at the restart of the spinning operation. Thus, according to the present invention, the yarn end portion is kept in a deflected position as it is taken out of the rotor at the cessation of the spinning, and stopped so that the yarn end is disposed within a spinning tube provided in direct adjacency to the spinning rotor. At the restart of the winding operation, the yarn end portion is again straightened and inserted into the rotor as end yarn so as to be pieced up with the sliver. In order that the yarn end portion may not be thrown out of the spinning tube due to twist shrinkage, a yarn grip piece is provided to the upper end of a braking lever designed to apply a braking force to the combing roller.
At this time, if the end yarn should be supplied into the rotor at an excess speed, it may be subjected to a slight oscillation or travel in a zigzag line and thus the yarn may be pieced to the sliver in a disorderly state. According to the present invention, it is possible to control the supply speed of the yarn end portion to be lower than the speed of suction air current provided in the spinning tube so that the yarn end portion may be supplied in a taut state into the rotating rotor.
In addition, the present invention provides an apparatus wherein a single drive shaft is connected to a common driving shaft for the wind-up packages of the respective spinning units through a first clutch and also to a drive device for a yarn deflective rod through a second or a reversible clutch, whereby said rod may be reciprocated or stopped so as to deflect the yarn end portion at the cessation of spinning or straighten it up at the restart of the spinning. Such apparatus is especially convenient for a spinning system wherein a number of the spinning units of the system are started or stopped simultaneously.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an explanatory view showing the shape of the terminal portion of the spun yarn obtained in the conventional method;
FIG. 2 is a similar view to FIG. 1 showing the shape of the terminal portion of the spun yarn obtained in the inventive method;
FIG. 3 is a partial diagrammatic view showing a spinning unit in accordance with the present apparatus;
FIG. 4 is a partial plan view showing the braking device for the combing roller in accordance with the present invention;
FIG. 5 is a sectional view taken along line V -- V of FIG. 4;
FIG. 6 is a front view showing the yarn deflective device in accordance with the present invention; and
FIG. 7 is a diagram for explanation of the operation of the present apparatus.
DETAILED DESCRIPTION OF THE INVENTION
Reference in now had to the accompanying drawings for illustration of a preferred embodiment of the present invention.
Referring to FIG. 3, the fiber supplied by a feed roll 1 is opened by a combing roller 3 and supplied into a spinning rotor 4 where the fiber is spun into a yarn with rotation of the rotor 4. The spun yarn is fed through a spinning tube 5 and wound up on a package 7 as it is imparted a traverse motion at a drum 6. A braking lever for braking the combing roller 3 is shown at 8 and is journaled at one end by a pivot pin 9 and provided with a boss 10 at the other end for engagement with a spring 11 and an actuating arm provided to a solenoid 12. During the spinning operation, the solenoid 12 is usually energized and thus the braking force is not applied to the combing roller. Upon cessation of the spinning, the solenoid 12 is de-energized. Thus, a brake shoe 13 provided to the braking lever 8 is pressed onto a shaft 14 of the combing roller 3, under the force of the compression spring 11, so as to brake the combing roller. The numeral 15 denotes a grip lever secured to the braking lever 8 and provided with a yarn grip piece 16 which is located at the exit of the spinning tube 5. As the braking lever 8 is pivoted about pivot pin 9 for braking the combing roller, said grip lever 15 is also pivoted concurrently with the braking lever 8 so that the spun yarn 18 is gripped between the yarn grip piece 16 and a fixed stopper 17. The grip lever 15 is preferably a leaf spring in order to resiliently grip the yarn 18 by the yarn piece 16 and the fixed stopper 17.
Although a single spinning unit is shown in FIG. 3, usually a large number of the spinning units as shown in FIG. 3 are arranged in parallel in a single spinning system. In a modified embodiment shown in FIGS. 4 and 5, the solenoids 12 of the spinning units can be actuated simultaneously for simultaneously braking the combing rollers of all of the spinning units. Referring to FIGS. 4 and 5, a braking lever 108 is mounted pivotally by a pivot pin 109 as in the preceding embodiment of FIG. 3. Said lever 108 is associated at the other end with a spring 121 and thereby urged into pressure contact with a cam 120 secured to a common cam shaft 119 for a number of the spinning units. Said cam shaft extends in the array direction of the spinning units. Thus, with rotation of the cam shaft 119, each braking lever 108 is pivoted gradually so that the brake shoe 113 associated therewith is brought into pressure contact with a shaft 114 of a combing roller 103 of each spinning unit for simultaneously braking all the combing rolls of the spinning system. The rotor or spinning chamber is shown schematically at 104. The cam 120 has such a profile that the cam surface thereof is elevated gradually to the point of maximum height and then lowered suddenly to the point of minimum height as measured from its inner surface. Due to such cam profile, the braking lever 108 is returned from the braking position to the non-braking position as the contact point of the end of the brake lever 108 with the cam surface is shifted from said point of the minimum height to said point of the maximum height. The shafts 114 of the respective spinning units are driven by a common driving shaft 122 by way of a transmission belt 123. A tension pulley 124 for the belt 123 is journaled at the end part of a lever 126 which is associated with a spring 125.
The yarn deflecting mechanism is shown in detail in FIG. 6. A first clutch 229 and a second or reversible clutch 230 are mounted to a driving shaft 228. A drum shaft 227 carrying a number of drums 206 of the respective spinning units is connected to the first clutch 229, while the second clutch 230 is associated by way of a transmission belt 234 with a pulley 233 associated in turn with the end of a deviating rod 232 which is fitted securely with a number of deviating guides 231 for the respective spinning units.
The numeral 235 designates a weight mass connected to the other end of the yarn deflective rod 232, and the numerals 236, 237 designate a pair of microswitches associated with the second clutch 230. These microswitches, when pressed by a dog 238 secured to the rod 238, will operate so as to disconnect said second clutch to stop the movement of the rod 238 at the two predetermined limit positions. The numeral 207 designates a yarn winding package, the numerals 239, 240 designate yarn guides and the numeral 205 designates a spinning tube. The driving shaft 228 is connected, by way of a gearing, not shown, to a drive device for a transmission belt, also not shown, for driving the rotor 204 into rotation.
The operation of the present apparatus will be described below by referring mainly to FIG. 7. In the diagram of FIG. 7, I is an electrical source which is switched on or off in accordance with the desired operation of the spinning system and II to VII show the stop and restart of each means of the invention respectively. That is, II is an operation of the rotor; III is that of the drum or package; IV is that of the feed roller; V is that of the combing roller; VI is that of the yarn deflective guide; and VII is the suction means.
When the spinning units are disconnected from an electrical source at a time T the rotor 104, the drum 206 and the feed roll 101 are decelerated gradually and brought to a halt after lapse of a time interval T 1 . During the inertia rotation and after lapse of a further time interval T 2 , the rotation of the feed roll 101 and that of the driving shaft 122 are stopped, at the same time that rotation of the combing rollers of the spinning units is terminated suddenly and unanimously due to actuation of the braking lever 108. The supply of the fiber into the spinning rotor is now terminated. After lapse of time interval T 3 , the first clutch 229 is disconnected, and the drums 206 are brought to a stop suddenly by the operation of a braking device, not shown, provided in the clutch 229. Rotation of the package 207 connected to each drum 206 is also terminated. At this time, the second or reversible clutch 230 is connected to the forward side by an output signal from an AND gate (not shown) to the input terminals of which are supplied an input signal from the microswitch 237 which is turned on by engagement with the dog 238 and an input instruction signal for stopping the spinning operation. The yarn deflective rod 232 is now moved towards the right in FIG. 6, due to the forward revolution of the output shaft of the second clutch 230. The spun yarn is deflected from its normal path by engagement with the yarn deflective guide 231. As the rod 232 is moved further and the microswitch 236 is acted upon by the dog 238, the translatory movement of the deflective rod 232 is terminated upon disengagement of the second clutch.
If the yarn deflective guide 231 is moved at this time so that the spun yarn is withdrawn from the rotor 204 at a variable yarn speed in proportion to the decreasing rotor speed, that is, maintaining the same ratio of the normal take out speed to the number of the rotation of the rotor, the yarn end may have a number of twists per unit yarn length equal to that obtained during the normal spinning. This variable take-out speed can be set by proper selection of the speed reducing ratio of the pulleys 241, 242 designed to transmit the rotation of the driving shaft 228 to the output side of the second clutch 230. After this operation, the air suction unit associated with the spinning rotor is switched off.
When restaring the spinning operation, the electrical source is switched on after lapse of time interval T' from the starting time of the suction unit. Thus the spinning rotor 104 is started and driven at a gradually increasing speed. After lapse of time interval T 4 , the braking lever 108 is disengaged from the combing roller 103, whilst the driving shaft 122 is driven into rotation, so that the combing roller 103 starts again to rotate. After time interval T 5 when the rotor 104 has attained a speed sufficient for piecing up the yarn to the sliver, the instruction signal for restarting the spinning operation is applied to an input terminal of the AND gate (not shown) to the other input terminal of which is also supplied a signal from the microswitch 236 which is turned on by engagement with the dog 238 during the cessation of spinning. The output signal from the AND gate is supplied to the reversible clutch 230 as that the latter is connected for reverse rotation of the output shaft. Thus the yarn deflective rod 232 is moved towards left in FIG. 6. The spun yarn, thus far gripped by the yarn deflective guide 231, is now released and inserted into the inside of the spinning rotor 204 as an end yarn. At this time, the yarn deflective rod 232 is moved at a speed such that the end yarn may be inserted into the rotor 204 at a slower rate than that of the suction air current pervailing in the suction tube 205.
Thus the end yarn may be inserted in a straight position into the rotor. To this end, the suction force of the air suction unit may be adjusted relatively to the rightward movement of the rod 232. As the microswitch 237 is pressed by the dog 238, the second clutch 230 is switched to its neutral position so that rightward movement of the deflective rod 232 is now terminated. After lapse of a time interval T 6 from the time of insertion of the end yarn, the feed roller 101 is started again to start the supply of the fiber. After lapse of a further interval time T 7 , the clutch 229 is engaged again to start the rotation of the drum 206 and the winding of the spun yarn. The spinning operation will be continued at a working speed after lapse of a time interval T 8 from the time of starting of the spinning rotor.
The above time intervals for the start and termination of the various elements may be set by using the conventional timing devices.
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The present invention relates to an open-end spinning system and more particularly to a method and an apparatus for stopping and starting the spinning operation of the open-end spinning system in such a way that the end portion of the spun yarn of the previous spinning may be used as it is as the piecing-up end yarn for the following spinning operation. The apparatus of the present invention, includes means for positively braking the combing roller for concurrently and suddenly stopping the rotation of the combing roller and the feed roller and means for taking the end portion of the spun yarn out of the spinning rotor, maintaining the taken out portion in a deflected state with the end of the yarn disposed within a spinning tube, and releasing the yarn at the restart of the spinning operation so that said end portion may be injected into the spinning rotor.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a fluid dynamic bearing unit.
[0003] 2. Description of the Related Art
[0004] Fluid dynamic bearing units support a shaft member without contact by a fluid's dynamic pressure effect occurring in their bearing clearances. Having such characteristics as high-speed rotation, high rotation accuracy, and low vibration, bearing units of this type are suitably used in motors that are mounted on various types of electric apparatuses including information devices. More specifically, they are used as spindle-motor bearing units in magnetic disk drives such as HDD, optical disc drives such as CD-ROM, CD-R/RW, and DVD-ROM/RAM, and magneto-optical disc drives such as MD and MO, and motor bearing units in polygon scanner motors of laser beam printers (LBP), color wheel motors of projectors, fan motors, and the like.
[0005] For example, a fluid dynamic bearing unit to be built in a spindle motor of a disk drive such as HDD has a radial bearing portion for supporting a shaft member in radial directions and a thrust bearing portion for supporting the shaft member in thrust directions, both of which may be configured as fluid dynamic bearings. Among the known examples of the radial bearing portion in this type of fluid dynamic bearing unit are ones in which dynamic pressure generating grooves are formed as a dynamic pressure generating portion in either one of the inner periphery of a bearing sleeve and the opposed outer periphery of a shaft member, with a radial bearing clearance between the two peripheries (for example, see Japanese Patent Application Laid-Open No. 2003-239951).
[0006] Now, information devices that incorporate fluid dynamic bearing units of the foregoing configuration, such as HDD or other disk drives, require even faster rotations for the sake of a further increase in read speed. This increases a moment load to act on the bearing portions that rotatably support the spindle shaft. To address this increased moment load, it is necessary to provide a plurality of radial bearing portions at axially separated positions, with an increased span between the radial bearing portions. In a conventional configuration, the plurality of radial bearing portions are formed on the inner side of a single bearing sleeve. Due to demands for motors of smaller sizes and for spindle shafts and bearing sleeves of accordingly smaller diameters, however, it is sometimes difficult to manufacture a bearing sleeve that is capable of an increased span between the radial bearing portions.
[0007] As means for increasing the span between the radial bearing portions and facilitating the manufacturing of the bearing sleeve as well, a plurality of bearing sleeves may be arranged in a plurality of positions axially separated from each other (for example, see the publication of Japanese Patent No. 3602707).
[0008] To arrange the bearing sleeves in a plurality of positions, each of the bearing sleeves is fixed to the inner periphery of the housing by adhesion, press fit, and the like. With adhesion, however, the fixing operation takes a lot of time and labor since the adhesion process must be carefully performed so that fluid channels for a lubricating fluid, formed in the outer peripheries of the bearing sleeves, may not be filled up with the adhesive. For press fit, sufficient fixing power is secured by increasing the interference between the outer peripheries of the bearing sleeves and the inner periphery of the housing. This narrows the inside diameter of the bearing sleeves with a decrease in the radial bearing clearances, possibly causing unfavorable effects on the radial bearing performance such as an increased torque loss. There is thus the need for improvements in terms of the fixing operation of the bearing sleeves and the provision of the fixing power.
[0009] Moreover, even when any of the foregoing fixing means including adhesion, press fit, and the like is employed, if the housing has a coefficient of linear expansion greater than that of the bearing sleeves, the bearing sleeves undergo a compressive force from the housing to shrink in the inside diameter due to a difference in thermal contraction between the members with decreasing temperature. This can produce unfavorable effects on the radial bearing performance for the same reason as mentioned above.
SUMMARY OF THE INVENTION
[0010] A first object of the present invention is to provide a fluid dynamic bearing unit which has a high load capacity against a moment load, whose bearing sleeve can be manufactured and fixed easily, and which can provide a required fixing power.
[0011] A second object of the present invention is to provide a fluid dynamic bearing unit which has a high load capacity against a moment load, whose bearing sleeve can be manufactured and fixed easily, and which can provide a required fixing power without causing a reduction in the inside diameter of the bearing sleeve. Yet another object is to provide a fluid dynamic bearing unit which can prevent or suppress a reduction in the inside diameter of the bearing sleeve, and the resulting decrease of the radial bearing clearance as well, due to a difference in thermal contraction between the two members with decreasing temperature even if the housing has a coefficient of linear expansion greater than that of the bearing sleeve.
[0012] To achieve the foregoing first object, a first aspect of the present invention provides a fluid dynamic bearing unit including: a housing; a bearing sleeve accommodated in the housing; a shaft member inserted into an inner periphery of the bearing sleeve; and a radial bearing portion for supporting the shaft member in a radial direction without contact by a dynamic pressure effect of a lubricating fluid occurring in a radial bearing clearance between the inner periphery of the bearing sleeve and an outer periphery of the shaft member. The fluid dynamic bearing unit is characterized in that the bearing sleeve comprises a plurality of bearing sleeves which are arranged so as to be axially separated from each other, that a spacer part is arranged between the axially-separated bearing sleeves, that the spacer part is stationarily arranged on the housing, and that the bearing sleeves are fixed to the spacer part by adhesion at their respective ends opposed to ends of the spacer part.
[0013] According to this first aspect, a plurality of bearing sleeves are arranged in a plurality of positions axially separated from each other. This can increase the span between the radial bearing portions to improve the load capacity against a moment load, and facilitate the manufacturing of the bearing sleeves. The bearing sleeves are fixed to the ends of the space part, which is stationarily arranged on the housing, by adhesion at their respective ends opposed to the ends of the spacer part. This eliminates the possibility that the adhesive may fill up fluid channels for the lubricating fluid that are formed in the outer peripheries of the bearing sleeves if any. A fixing power necessary for the bearing sleeves can also be provided.
[0014] To achieve the foregoing second object, second aspect of the present invention provides a fluid dynamic bearing unit including: a housing; a bearing sleeve accommodated in the housing; a shaft member inserted into an inner periphery of the bearing sleeve; and a radial bearing portion for supporting a shaft member in a radial direction without contact by a dynamic pressure effect of a lubricating fluid occurring in a radial bearing clearance between the inner periphery of the bearing sleeve and an outer periphery of the shaft member. The fluid dynamic bearing unit is characterized in that the bearing sleeve comprises a plurality of bearing sleeves which are arranged so as to be axially separated from each other, that a spacer part is formed between the axially-separated bearing sleeves, that the spacer part is stationarily arranged on the housing, and that the bearing sleeves are inserted into an inner periphery of the housing with a gap, and are fixed to the spacer part by adhesion at their respective ends opposed to ends of the spacer part.
[0015] According to this second aspect, a plurality of bearing sleeves are arranged in a plurality of positions axially separated from each other. This can increase the span between the radial bearing portions to improve the load capacity against a moment load, and facilitate the manufacturing of the bearing sleeves. The bearing sleeves are inserted into the inner periphery of the housing with a gap, and are fixed to the ends of the space part, which is stationarily arranged on the housing, by adhesion at their respective ends opposed to the ends of the spacer part. This eliminates the possibility that the adhesive may fill up fluid channels for the lubricating fluid that are formed in the outer peripheries of the bearing sleeves if any. A fixing power necessary for the bearing sleeves can also be provided without causing a reduction in the inside diameter of the bearing sleeves. In addition, even if the housing has a coefficient of linear expansion greater than that of the bearing sleeves, some or all of the difference in thermal contraction between the members with decreasing temperature is absorbed by the gaps between the outer peripheries of the bearing sleeves and the inner periphery of the housing. This prevents or suppresses a reduction in the inside diameter of the bearing sleeves ascribable to the difference in thermal contraction between the members, and the resulting decrease of the radial bearing clearances.
[0016] To arrange the spacer part stationarily on the housing, the foregoing first and second aspects shall each cover the configurations that the spacer part is integrally formed on the housing, and that a separate spacer part is fixed to the housing by appropriate means such as adhesion, press fit, press-fit adhesion (the combined use of press fit and adhesion), and welding.
[0017] In the foregoing first and second aspects, recess-like adhesion pockets are preferably formed in at least either the ends of the bearing sleeves or the ends of the spacer part. The adhesive pockets can capture some of the adhesive that is filled or applied to between the ends of the bearing sleeves and the ends of the spacer part, thereby avoiding the phenomenon that an excess of the adhesive flows radially inward to reach the inner peripheries of the bearing sleeves (the radial bearing clearances).
[0018] In the first and second aspects, the spacer part may have a fluid channel opened to both axial sides. The fluid channel in the spacer part may also be put into communication with axial fluid channels formed between the inner periphery of the housing and the outer peripheries of the bearing sleeves. These fluid channels constitute a circulation channel for letting the lubricating fluid flow and circulate inside the housing. The lubricating fluid flows and circulates through this circulation channel, whereby the lubricating fluid filled in the internal space of the housing, including the bearing clearances, is maintained in favorable pressure balance. This also prevents the production of bubbles due to the occurrence of a local negative pressure, as well as the leakage of the lubricating fluid, the production of vibrations, and other problems ascribable to the production of bubbles. Since the circulation channel comes to open-air sides in part, air bubbles, if any, that get into the lubricating fluid for any reason can be emitted to the open-air sides while circulating with the lubricating fluid. This prevents the adverse effects of bubbles more effectively.
[0019] In the foregoing first and second aspects, the shaft member may have a protrusion part protruding axially outward, and a thrust bearing portion for supporting the shaft member in a thrust direction without contact by a dynamic pressure effect of the lubricating fluid occurring in a thrust bearing clearance may be formed between an end of the protrusion part and an end of one of the bearing sleeves. The protrusion part may be integrally formed on the shaft member, or may be fixed to the shaft member. Dynamic pressure generating means (such as dynamic pressure generating grooves) of the thrust bearing portion may be formed in either the end of the protrusion or the end of the bearing sleeve.
[0020] In this case, a seal space may be formed radially outside the foregoing protrusion part of the shaft member. This seal space has the function of absorbing a volume change (expansion and contraction) of the lubricating fluid filled in the internal space of the housing due to temperature variations, i.e., a so-called buffer function.
[0021] In the foregoing first and second aspects, the housing may be an article die-molded from a molten material. The housing may be made of either a resin material or a metal material. If the housing is made of a resin material, for example, a thermoplastic resin or the like may be injection molded. If the housing is made of a metal material, for example, an aluminum alloy, a magnesium alloy, stainless steel, or the like may be die cast or injection molded (by so-called MIM or thixomolding).
[0022] The fluid dynamic bearing unit according to the foregoing first aspect is suitably used in a motor that is built in a disk drive such as HDD, or a server HDD in particular.
[0023] The fluid dynamic bearing unit according to the foregoing second aspect is suitably used in a motor that is built in a disk drive such as HDD.
[0024] According to the first aspect, it is possible to provide a fluid dynamic bearing unit which has a high load capacity against a moment load, whose bearing sleeves can be manufactured and fixed easily, and which can provide a required fixing power.
[0025] According to the second aspect, it is possible to provide a fluid dynamic bearing unit which has a high load capacity against a moment load, whose bearing sleeves can be manufactured and fixed easily, and which can provide a required fixing power without causing a reduction in the inside diameter of the bearing sleeves. In addition, it is possible to prevent or suppress a reduction in the inside diameter of the bearing sleeves, and the resulting decrease of the radial bearing clearances as well, due to a difference in thermal contraction between the members with decreasing temperature even if the housing has a coefficient of linear expansion higher than that of the bearing sleeves.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 is a sectional view of a fluid dynamic bearing unit according to a first embodiment;
[0027] FIGS. 2A , 2 B, and 2 C are a top view, sectional view, and bottom view, respectively, showing a state where bearing sleeves are fixed to a housing;
[0028] FIG. 3 is an enlarged sectional view showing an upper area of the housing;
[0029] FIG. 4 is an enlarged sectional view showing the vicinities of locations where the bearing sleeves and a spacer part are fixed to each other by adhesion;
[0030] FIG. 5 is a sectional view of a fluid dynamic bearing unit according to a second embodiment;
[0031] FIG. 6 is a sectional view of a fluid dynamic bearing unit according to a third embodiment;
[0032] FIG. 7 is a sectional view of a fluid dynamic bearing unit according to a fourth embodiment;
[0033] FIGS. 8A , 8 B, and 8 C are a top view, sectional view, and bottom view, respectively, showing a state where bearing sleeves are fixed to a housing;
[0034] FIG. 9 is an enlarged sectional view showing an upper area of the housing;
[0035] FIG. 10 is an enlarged sectional view showing the vicinities of locations where the bearing sleeves and a spacer part are fixed to each other by adhesion;
[0036] FIG. 11 is a sectional view of a fluid dynamic bearing unit according to a fifth embodiment; and
[0037] FIG. 12 is a sectional view of a fluid dynamic bearing unit according to a sixth embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0038] Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0039] FIG. 1 shows a fluid dynamic bearing unit 1 according to a first embodiment. This fluid dynamic bearing unit 1 supports rotation of a spindle shaft of a motor to be built in a HDD, for example, or a server HDD in particular. This fluid dynamic bearing unit 1 includes, as its primary components: a housing 2 ; a plurality of, for example, two bearing sleeves 3 and 4 which are accommodated in the housing 2 at positions axially separated from each other; and a shaft member 5 which is inserted into the inner peripheries of the bearing sleeves 3 and 4 .
[0040] As will be described later, a first radial bearing portion R 1 is formed between the inner periphery 3 a of the bearing sleeve 3 and the outer periphery 5 a of the shaft member 5 . A second radial bearing portion R 2 is formed between the inner periphery 4 a of the bearing sleeve 4 and the outer periphery 5 a of the shaft part 5 . Moreover, in this embodiment, a first thrust bearing portion T 1 is formed between the top end 3 b of the bearing sleeve 3 and the bottom end 6 b of a seal member 6 . A second thrust bearing portion T 2 is formed between the bottom end 4 b of the bearing sleeve 4 and the top end 7 b of a seal member 7 . For convenience of explanation, the following description will be given with the side where an end of the shaft member 5 protrudes from the housing 2 (the top side of the diagram) as top side, and with the axially opposite side as bottom side.
[0041] The housing 2 is integrally formed, for example, by injection molding a resin material. It has the inner peripheries 2 a and 2 b in which the bearing sleeves 3 and 4 are accommodated, and a spacer part 2 c which protrudes radially inward from the inner peripheries 2 a and 2 b. The inner peripheries 2 a and 2 b lie in positions axially separated from each other, corresponding to the positions where the bearing sleeves 3 and 4 are arranged. The area between the inner peripheries 2 a and 2 b is the spacer part 2 c. Note that the inner peripheries 2 a and 2 b have the same diameter. In this embodiment, the spacer part 2 c has axial fluid channels 2 c 1 . The fluid channels 2 c 1 are opened to both the top end 2 c 2 and the bottom end 2 c 3 of the spacer part 2 c. There are formed a plurality of, for example, three fluid channels 2 c 1 at regular circumferential intervals. Large diameter portions 2 d and 2 e are also formed at both ends of the housing 2 . The large diameter portions 2 d and 2 e communicate with the inner peripheries 2 a and 2 b through step surfaces 2 f and 2 g, respectively.
[0042] The fluid channels 2 c 1 of the spacer part 2 c may be formed by applying hole machining after the housing 2 is molded. For the sake of reduced machining man-hours and the resulting reduction in the manufacturing cost, however, they are preferably molded simultaneously with the molding of the housing 2 . This can be achieved by providing molding pins corresponding to the shapes of the fluid channels 2 c 1 on the molding die for the housing 2 to be molded in. The fluid channels 2 c 1 are not limited to circular cross sections and may have noncircular shapes (such as elliptic and polygonal). Furthermore, the fluid channels 2 c 1 need not have a constant cross-sectional area across the axial direction. For example, some portions may have relatively greater cross-sectional areas, and others relatively smaller cross-sectional areas.
[0043] The housing 2 is made primarily of thermoplastic resin. Examples of available resins include amorphous resins such as polysulfone (PSU), polyethersulfone (PES), polyphenylsulfone (PPSU), and polyetherimide (PEI), and crystalline resins such as liquid crystal polymer (LCP), polyetheretherketone (PEEK), polybutylene terephthalate (PBT), and polyphenylene sulfide (PPS). The types of fillers for filling the foregoing resin are not limited in particular, either. Examples of available fillers include fibrous fillers such as glass fiber, whisker-like fillers such as potassium titanate, scale-like fillers such as mica, and fibrous or powder conductive fillers such as carbon fiber, carbon black, graphite, carbon nanomaterials, and metal powders. These fillers each may be used alone, or two or more types may be mixed in use. In this embodiment, the housing 2 is made of a resin material that is composed of liquid crystal polymer (LCP) as a crystalline resin and 2% to 8% by weight of carbon fibers or carbon nanotubes as a conductive filler.
[0044] The shaft member 5 is made of metal a material such as stainless steel, is shaped into a shaft of generally uniform diameter on the whole. In this embodiment, the seal members 6 and 7 of annular shape are also fixed to the shaft member 5 by appropriate fixing means such as adhesion and press-fit adhesion (the combined use of press fit and adhesion). These seal members 6 and 7 are shaped to protrude radially outward from the outer periphery 5 a of the shaft member 5 , and are accommodated in the large diameter portions 2 d and 2 e of the housing 2 , respectively. To improve the fixing strength of the adhesive, circumferential grooves 5 a 1 and 5 a 2 , or adhesive pockets, are formed in the outer periphery 5 a of the shaft member 5 at positions where the seal members 6 and 7 are fixed to. The seal members 6 and 7 may be made of brass or other soft metal materials, or other metal materials, or may be made of resin materials. Either one of the seal members 6 and 7 may be formed integrally with the shaft member 5 . In this case, the assembly consisting of the shaft member 5 and the one seal member may be formed as a composite body of metal and resin. In one possible example, the shaft member 5 is made of metal, and the one seal member is insert molded using resin.
[0045] The outer periphery 6 a of the seal member 6 and the large diameter portion 2 d of the housing 2 create a seal space S 1 of predetermined capacity therebetween. The outer periphery 7 a of the seal member 7 and the large diameter portion 2 e of the housing 2 create a seal space S 2 of predetermined capacity therebetween. In this embodiment, the outer periphery 6 a of the seal member 6 and the outer periphery 7 a of the seal member 7 are shaped into tapered surfaces which gradually decrease in diameter toward the respective outer sides of the housing 2 . Consequently, both the seal spaces S 1 and S 2 have a tapered shape such that they gradually decrease toward the inside of the housing 2 .
[0046] The bearing sleeves 3 and 4 are formed in a cylindrical shape out of a porous body of sintered metal, for example, or a porous body of sintered metal mainly composed of copper in particular. The bearing sleeves 3 and 4 are inserted into the inner peripheries 2 a and 2 b of the housing 2 , respectively, or press fitted therein with a pressing force not as high as deforms the inner peripheries 3 a and 4 a (light press fit).
[0047] As shown enlarged in FIG. 4 , the bottom end 3 c of the bearing sleeve 3 is then fixed to the top end 2 c 2 of the spacer part 2 c with an adhesive A 1 . The bottom end 3 c of the bearing sleeve 3 has an adhesive pocket 3 c 1 of circumferential groove shape. Some of the adhesive A 1 gets into the adhesive pocket 3 c 1 , which precludes the phenomenon that an excess of the adhesive A 1 flows radially inward to reach-the inner periphery 3 a of the bearing sleeve 3 (the radial bearing clearance). The bottom end 3 c may have a plurality of circumferential grooves or adhesive pockets 3 c 1 . Note that the bottom end 3 c has a chamfer 3 c 2 on its inner side, and this chamfer 3 c 2 also contributes to preventing the adhesive A 1 from reaching the radial inner side. The bottom end 3 c of the bearing sleeve 3 preferably has a surface pore ratio lower than that of the outer periphery 3 d, so that it becomes difficult for the adhesive A 1 to reach the inside of the bearing sleeve 3 through the surface pores of the bottom end 3 c. The recessed adhesive pocket may be formed in the top end 2 c 2 of the spacer part 2 c, or both in the bottom end 3 c of the bearing sleeve 3 and the top end 2 c 2 of the spacer part 2 c.
[0048] Similarly, the top end 4 c of the bearing sleeve 4 is fixed to the bottom end 2 c 3 of the spacer part 2 c with an adhesive A 2 . The top end 4 c of the bearing sleeve 4 has an adhesive pocket 4 c 1 of circumferential groove shape. Some of the adhesive A 2 gets into the adhesive pocket 4 c 1 , which prevents the phenomenon that an excess of the adhesive A 2 flows radially inward to reach the inner periphery 4 a of the bearing sleeve 4 (the radial bearing clearance) The top end 4 c may have a plurality of circumferential grooves or adhesive pockets 4 c 1 . Note that the bottom end 4 c has a chamfer 4 c 2 on its inner side, and this chamfer 4 c 2 also contributes to preventing the adhesive A 2 from reaching the radial inner side. The top end 4 c of the bearing sleeve 4 preferably has a surface pore ratio lower than that of the outer periphery 4 d, so that it becomes difficult for the adhesive A 2 to reach the inside of the bearing sleeve 4 through the surface pores of the top end 4 c. The recessed adhesive pocket may be formed in the bottom end 2 c 3 of the spacer part 2 c, or both in the top end 4 c of the bearing sleeve 4 and the bottom end 2 c 3 of the spacer part 2 c.
[0049] As shown in FIGS. 2A to 2C , the bearing sleeve 3 has dynamic pressure generating grooves 3 a 1 of herringbone shape in the inner periphery 3 a where to make the radial bearing surface of the first radial bearing portion R 1 , dynamic pressure generating grooves 3 b 1 of herringbone shape in the top end 3 b where to make the thrust bearing surface of the first thrust bearing portion T 1 , and axial grooves 3 d 1 in the outer periphery 3 d. There are formed a plurality of, for example, three axial grooves 3 d 1 at regular circumferential intervals. These axial grooves 3 d 1 and the inner periphery 2 a of the housing 2 create axial fluid channels therebetween. Similarly, the bearing sleeve 4 has dynamic pressure generating grooves 4 a 1 of herringbone shape in the inner periphery 4 a where to make the radial bearing surface of the second radial bearing portion R 2 , dynamic pressure generating grooves 4 b 1 of herringbone shape in the bottom end 4 b where to make the thrust bearing surface of the second thrust bearing portion T 2 , and axial grooves 4 d 1 in the outer periphery 4 d. There are formed a plurality of, for example, three axial grooves 4 d 1 at regular circumferential intervals. These axial grooves 4 d 1 and the inner periphery 2 b of the housing 2 create axial fluid channels therebetween.
[0050] As shown enlarged in FIG. 3 , the bearing sleeve 3 is fixed to the top end 2 c 2 of the spacer part 2 c with the adhesive A 1 so that the top end 3 b is flush with the upper step surface 2 f of the housing 2 or protrudes from the step surface 2 f by a small dimension δ 2 . This state can be achieved by controlling the axial dimension of the bearing sleeve 3 and the axial dimension of the inner periphery 2 a of the housing 2 (or the axial dimension of the spacer part 2 c ). As shown in the diagram, when the top end 3 b of the bearing sleeve 3 protrudes from the step surface 2 f by the dimension δ 2 , the axial dimension between the bottom end 6 b of the seal member 6 and the step surface 2 f exceeds the thrust bearing clearance δ 1 of the first thrust bearing portion T 1 . Although not shown in the drawings, the same holds for the bearing sleeve 4 .
[0051] This fluid dynamic bearing unit 1 is assembled, for example, in the following steps.
[0052] Initially, the adhesive A 1 is applied to the bottom end 3 c of the bearing sleeve 3 or the top end 2 c 2 of the spacer part 2 c. The bearing sleeve 3 is then inserted into the inner periphery 2 a of the housing 2 so that the bottom end 3 c of the bearing sleeve 3 comes into contact with the top end 2 c 2 of the spacer part 2 c with the adhesive A 1 therebetween. Here, the axial grooves 3 d 1 of the bearing sleeve 3 and the fluid channels 2 c 1 of the spacer part 2 c are positioned to each other. This establishes communication between the fluid channels formed by the axial grooves 3 d 1 and the fluid channels 2 c 1 of the spacer part 2 c.
[0053] Next, the adhesive A 2 is applied to the top end 4 c of the bearing sleeve 4 or the bottom end 2 c 3 of the spacer part 2 c. The bearing sleeve 4 is then inserted into the inner periphery 2 b of the housing 2 so that the top end 4 c of the bearing sleeve 4 comes into contact with the bottom end 2 c 3 of the spacer part 2 c with the adhesive A 2 therebetween. Here, the axial grooves 4 d 1 of the bearing sleeve 4 and the fluid channels 2 c 1 of the spacer part 2 c are positioned to each other. This establishes communication between the fluid channels formed by the axial grooves 4 d 1 and the fluid channels 2 c 1 of the spacer part 2 c.
[0054] The adhesives A 1 and A 2 are then cured to form the assembly of the housing 2 and the bearing sleeves 3 and 4 as shown in FIGS. 2A to 2C .
[0055] Subsequently, the shaft member 5 is inserted into the inner peripheries 3 a and 4 a of the bearing sleeves 3 and 4 and the inner periphery 2 c 4 of the spacer part 2 c. The seal members 6 and 7 are fixed to the predetermined positions of the shaft member 5 . Note that one of the seal members 6 and 7 may be previously fixed to the shaft member 5 before the insertion, or may be formed integrally with the shaft member 5 .
[0056] After the assembly is completed through the foregoing steps, a lubricating fluid, for example, lubricating oil is filled into the internal space of the housing 2 that is sealed with the seal members 6 and 7 , including the internal pores of the bearing sleeves 3 and 4 (the internal pores in the porous body texture). The lubricating oil can be filled, for example, by immersing the assembled fluid bearing unit 1 into the lubricating oil in a vacuum bath, and then releasing it to the atmospheric pressure.
[0057] When the shaft member 5 is rotated, the inner periphery 3 a of the bearing sleeve 3 and the inner periphery 4 a of the bearing sleeve 4 are opposed to the outer periphery 5 a of the shaft member 5 across respective radial bearing clearances. The gap between the inner periphery 2 c 4 of the spacer part 2 c and the outer periphery 5 a of the shaft member 5 is greater than the foregoing radial bearing clearances. The top end 3 b of the bearing sleeve 3 is opposed to the bottom end 6 b of the seal member 6 across a thrust bearing clearance. The bottom end 4 b of the bearing sleeve 4 is opposed to the top end 7 b of the seal member 7 across a thrust bearing clearance. With the rotation of the shaft member 5 , a dynamic pressure of the lubricating oil occurs in the foregoing radial bearing clearances. The shaft member is then rotatably supported in the radial directions without contact by the films of the lubricating oil formed in the radial bearing clearances. This constitutes the first radial bearing portion R 1 and the second radial bearing portion R 2 which rotatably support the shaft member 5 in the radial directions without contact. In the meantime, a dynamic pressure of the lubricating oil also occurs in the foregoing thrust bearing clearances. The seal members 6 and 7 fixed to the shaft member 5 are then rotatably supported in the thrust directions without contact by the films of the lubricating oil formed in the thrust bearing clearances. This forms the first thrust bearing portion T 1 and the second thrust bearing portion T 2 which rotatably support the shaft member 5 in the thrust directions without contact.
[0058] As described above, the seal spaces S 1 and S 2 formed on the side of the outer periphery 6 a of the seal member 6 and on the side of the outer periphery 7 a of the seal member 7 have the tapered shapes, gradually decreasing toward the inside of the housing 2 . The lubricating oil in both the seal spaces S 1 and S 2 is thus drawn into directions where the seal spaces get narrower, by the drawing action from the capillary force and by the drawing action from the centrifugal force during rotation. This consequently prevents leakage of the lubricating oil from inside the housing 2 effectively. The seal spaces S 1 and S 2 also have the buffer function of absorbing a volume change of the lubricating oil filled in the internal space of the housing 2 ascribable to temperature variations. Within the intended range of temperature variations, the surfaces of the lubricating oil remain in the seal spaces S 1 and S 2 all the time.
[0059] In addition, a series of circulation channels is formed inside the housing 2 , including: the fluid channels formed by the axial grooves 3 d 1 of the bearing sleeve 3 ; the fluid channels formed by the axial grooves 4 d 1 of the bearing sleeve 4 ; the fluid channels 2 c 1 of the spacer part 2 c; all the bearing clearances (the radial bearing clearances of the first radial bearing portion R 1 and the second radial bearing portion R 2 , and the thrust bearing clearances of the first thrust bearing portion T 1 and the second thrust bearing portion T 2 ); and the gap between the inner periphery 2 c 4 of the spacer part 2 c and the outer periphery 5 a of the shaft member 5 . The lubricating oil filled in the internal space of the housing 2 then flows and circulates through these circulation channels, whereby the lubricating oil is maintained in favorable pressure balance. This also prevents the production of bubbles due to the occurrence of a local negative pressure, as well as the leakage of the lubricating oil, the production of vibrations, etc., ascribable to the production of bubbles. In addition, the fluid channels formed by the axial grooves 3 d 1 of the bearing sleeve 3 and the fluid channels formed by the axial grooves 4 d 1 of the bearing sleeve 4 communicate at either end with the respective open-air sides, i.e., the seal spaces S 1 and S 2 . Consequently, air bubbles, if any, that get into the lubricating oil for any reason can be emitted to the open-air sides while circulating with the lubricating oil. This prevents the adverse effects of bubbles more effectively.
[0060] FIG. 5 shows a fluid dynamic bearing unit 11 according to a second embodiment. This fluid dynamic bearing unit 11 differs from the fluid dynamic bearing unit 1 according to the foregoing first embodiment in that the spacer part 2 c is made of a sleeve-like member separate from the housing 2 , and this spacer part 2 c is fixed to the inner periphery 2 a of the housing 2 by appropriate means such as adhesion, press fit, and press-fit adhesion. The fluid channels 2 c 1 are formed in the outer periphery of the spacer part 2 c in the form of axial grooves. This spacer part 2 c may be made of a resin material the same as or different from that of the housing 2 , or a metal material. The inner periphery 2 a of the housing 2 has an axially straight shape between the locations where the bearing sleeve 3 is mounted on and where the bearing sleeve 4 is mounted on. As compared to the fluid dynamic bearing unit 1 of the first embodiment, the housing 2 is simplified in shape. In other respects, the same discussion applies as in the first embodiment. Substantially the same members or parts will thus be designated by like reference numerals, and redundant description will be omitted.
[0061] FIG. 6 shows a fluid dynamic bearing unit 21 according to a third embodiment. This fluid dynamic bearing unit 21 differs from the fluid dynamic bearing unit 1 according to the foregoing first embodiment in that the inner peripheries 2 a and 2 b of the housing 2 extend to the respective ends of the housing 2 with a uniform diameter, and that the seal members 6 and 7 have a relatively small diameter accordingly. This provides the advantage that the housing 2 can be simplified in shape and reduced in diameter as compared to the fluid dynamic bearing unit 1 of the first embodiment. In other respects, the same discussion applies as in the first embodiment. Substantially the same members or parts will thus be designated by like reference numerals, and redundant description will be omitted.
[0062] The foregoing first to third embodiments have dealt with the cases where the dynamic pressure generating grooves of herringbone shape are employed as the dynamic pressure generating means of the radial bearing portions R 1 and R 2 and the thrust bearing portions T 1 and T 2 . Dynamic pressure generating grooves of spiral shape or other shapes may also be used. Otherwise, so-called step bearings or multilobe bearings may be employed as the dynamic pressure generating means.
[0063] FIGS. 7 , 8 A to 8 C, 9 , and 10 show a fluid dynamic bearing unit 31 according to a fourth embodiment, respectively corresponding to FIGS. 1 , 2 A to 2 C, 3 , and 4 according to the foregoing first embodiment. This fluid dynamic bearing unit 31 supports rotation of a spindle shaft of a motor which is built in a HDD, for example. The fluid dynamic bearing unit 31 according to this fourth embodiment differs from the fluid dynamic bearing unit 1 according to the foregoing first embodiment in that the bearing sleeves 3 and 4 , which are formed in a cylindrical shape of a porous body of sintered metal, for example, or a porous body of sintered metal mainly composed of copper in particular, are inserted into the inner peripheries 2 a and 2 b of the housing 2 with small radial gaps C 1 and C 2 , respectively. These radial gaps C 1 and C 2 have such sizes as can absorb all the difference in thermal contraction between the resin housing 2 and the sintered metal bearing sleeves 3 and 4 ascribable to their different coefficients of linear expansion, for example, within the intended range of temperature variations. Note that the radial gaps C 1 and C 2 may be set to the same size or different sizes. In other respects, the same discussion applies as in the first embodiment. Substantially the same members or parts will thus be designated by like reference numerals, and redundant description will be omitted.
[0064] FIG. 11 shows a fluid dynamic bearing unit 41 according to a fifth embodiment. This fluid dynamic bearing unit 41 differs from the fluid dynamic bearing unit 31 according to the foregoing fourth embodiment in that the spacer part 2 c is made of a sleeve-like member separate from the housing 2 , and this spacer part 2 c is fixed to the inner periphery 2 a of the housing 2 by appropriate means such as adhesion, press fit, and press-fit adhesion. The fluid channels 2 c 1 are formed in the outer periphery of the spacer part 2 c in the form of axial grooves. This spacer part 2 c may be made of a resin material the same as or different from that of the housing 2 , or a metal material. The inner periphery 2 a of the housing 2 has an axially straight shape between the locations where the bearing sleeve 3 is mounted on and where the bearing sleeve 4 is mounted on. As compared to the fluid dynamic bearing unit 31 of the fourth embodiment, the housing 2 is simplified in shape. In other respects, the same discussion applies as in the fourth embodiment. Substantially the same members or parts will thus be designated by like reference numerals, and redundant description will be omitted.
[0065] FIG. 12 shows a fluid dynamic bearing unit 51 according to a sixth embodiment. This fluid dynamic bearing unit 51 differs from the fluid dynamic bearing unit 31 according to the foregoing fourth embodiment in that the inner peripheries 2 a and 2 b of the housing 2 extend to the respective ends of the housing 2 with a uniform diameter, and that the seal members 6 and 7 have a relatively small diameter accordingly. This provides the advantage that the housing 2 can be simplified in shape and reduced in diameter as compared to the fluid dynamic bearing unit 31 of the fourth embodiment. In other respects, the same discussion applies as in the fourth embodiment. Substantially the same members or parts will thus be designated by like reference numerals, and redundant description will be omitted.
[0066] The foregoing fourth to sixth embodiments have dealt with the cases where the dynamic pressure generating grooves of herringbone shape are employed as the dynamic pressure generating means of the radial bearing portions R 1 and R 2 and the thrust bearing portions T 1 and T 2 . Dynamic pressure generating grooves of spiral shape or other shapes may also be used, however. Otherwise, so-called step bearings or multilobe bearings may be employed as the dynamic pressure generating means.
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A fluid dynamic bearing unit is provided which has a high load capacity against a moment load, whose bearing sleeves can be manufactured and fixed easily, and which can provide a required fixing power. The bearing sleeve is inserted into an inner periphery of a housing, and its bottom end is fixed to the top end of a spacer part with an adhesive. Another bearing sleeve is inserted into another part of the inner periphery of the housing, and its top end is fixed to the bottom end of the spacer part with an adhesive.
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TECHNICAL FIELD
The present invention relates to machines to manufacture soap bars.
BACKGROUND OF THE INVENTION
Soap bars are manufactured by introducing into a die a block of relatively soft material from which the soap bar is to be formed. Typically, dies are provided with cavities trough which cooling water passes to cool the dies.
A problem with the above mentioned machines is that the soap bars formed frequently stick to the soap die because the current method of cooling has insufficient capacity and flow rate, particularly with glycerine/translucent soap. Still further, the above mentioned machines are relatively slow due to insufficient cooing capacity.
OBJECT OF THE INVENTION
It is the object of the present invention to overcome or substantially ameliorate the above discussed disadvantages.
SUMMARY OF THE INVENTION
There is disclosed herein a method to manufacture soap bars, said method including the steps of:
providing a first die member;
providing a second die member which co-operates with the first die member to provide a die cavity;
locating the die members so that they are spaced by a gap;
delivering to said gap a block of material from which the soap bar is to be formed;
bringing the die members together so that said material is enclosed in the cavity formed by the die members;
circulating a cooling fluid through the die members to cool the material;
separating the die members to expose the formed soap bar; and
ejecting the soap bar from between the die members; and wherein
said cooling fluid passes from a liquid phase to a gaseous phase within the die members.
There is further disclosed herein a machine to manufacture soap bars, said machine including:
a first die member;
a second die member to co-operate with the first die member to provide a die cavity;
means supporting the die members for relative movement therebetween a first position providing the die cavity and a second position at which the die members are spaced to permit material to form a soap bar to be delivered to a position between the die members and permit removal of a formed bar of soap; and
ducts within the die members through which a cooling fluid is to pass, said ducts including throttling means to cause expansion of the fluid within the die members, from a liquid phase to a gaseous phase.
Preferably, the above machine would have the ducts including passages extending to the exterior of the die members so that the cooling fluid vents to atmospheres surrounding the die members.
Preferably, the cooling fluid is nitrogen.
BRIEF DESCRIPTION OF THE DRAWINGS
A preferred form of the present invention will now be described by way of example with reference to the accompanying drawings wherein:
FIG. 1 is a schematic side elevation of a die assembly to manufacture soap bars;
FIG. 2 is a schematic top plan view of the die assembly of FIG. 1;
FIG. 3 is a schematic sectioned side elevation of the die assembly of FIGS. 1 and 2 sectioned along the line 3 — 3 ; and
FIG. 4 is a schematic sectioned side elevation of the die assembly of FIGS. 1 and 2 sectioned along the line 4 — 4 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the accompanying drawings there is schematically depicted a die assembly 10 . The die assembly 10 includes die blocks 11 and 12 supporting co-operating dies 13 and 14 . The dies 13 and 14 co-operate to provide a die cavity, 31 within which a soap bar is formed. The die block 11 and die 13 provide a first die member 15 while the die block 12 and die 14 provide a second die member 16 . The die members 15 and 16 are mounted so that relative movement therebetween can take place, The die members 15 and 16 are moveable from the position depicted to a position in which they are spaced permitting a formed soap bar to be removed from the cavity 15 and new soap material to be delivered thereto to be formed into a soap bar.
The die assembly 10 includes ducts through which a cooling fluid passes to lower the temperature of the disassembly 10 to aid in forming the soap bar. The ducts includes inlet ports 17 to which a supply of liquid nitrogen is attached. The inlet ports 17 lead to narrow passages 18 which throttle the liquid nitrogen causing it to expand. The expansion of the cooling fluid from a liquid phase to a gaseous phase requires latent heat of vaporization. Accordingly, the temperature of the die members 15 and 16 is lowered. The passages 18 lead to a chamber 19 in each of the dies 13 and 14 . The gas in the chambers 19 is allowed to exhaust via outlet passages 20 . Accordingly, the cooling fluid in its gaseous phase is allowed to provide a surrounding environment in respect of the dies 13 and 14 . This aids in reducing condensation and the formation of ice on the die members 15 and 16 and in particular the dies 13 and 14 .
Preferably, each of the dies 13 and 14 is provided with an ejector 21 moveable from its retracted position illustrated in FIG. 4, to an extended position 22 at which it would aid in ejecting a formed soap bar from the die cavity 31 . The ejector 21 includes a stem 23 having its extremity threaded and engaged with a nut 24 . The nut 24 attaches a piston 25 to the stem 13 , which piston 25 engages a spring which urges the piston 25 to move the ejector 21 to its retracted position.
The piston 25 co-operates with a cylindrical surface 29 to define a chamber 27 . The chamber 27 has extending to it a passage 28 . The passage 28 is attached to a supply of the cooling fluid (such as nitrogen). When cooling fluid of sufficient pressure is delivered to the chamber 27 the ejector 21 is moved to its extended position 22 to eject the formed soap bar. The cooling fluid delivered to the chamber 27 escapes through clearances between the piston 26 and surface 29 , and the ejector 21 and associated die 13 / 14 .
If so required, the die assembly 10 could be housed within an enclosure 30 to aid in retaining the gaseous cooling fluid around the die assembly 10 . This would also aid in insulating the die assembly 10 to maintain its low temperature and exclude atmospheric moisture from the die assembly 10 , thereby eliminating ice on the die blocks 11 and 12 .
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A machine and a method to manufacture soap bars. The machine and method involve a die assembly ( 10 ) having a pair of die blocks ( 11, 12 ) which support co-operating dies ( 13, 14 ). Liquid nitrogen is delivered to the two dies ( 13, 14 ) via a throttling passage ( 18 ) to cool the soap material being formed.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a control system of a coupling apparatus specifically of a rotary dobby loom, including a drive shaft, at least one eccentric hoop supported slidably or rotationally thereupon including a connecting rod arranged circumferentially therearound, which connecting rod is intended to be coupled to a member which is to be moved in a controlled manner, specifically a heald of a weaving machine, including further a dog which is supported in said eccentric hoop in a radially displaceable manner and is movable via operating and control means into engagement either into one of two recesses of the connecting rod or into one of two recesses of the drive shaft.
2. Description of the Prior Art
Modern dobby looms are based presently on electromagnetic control systems which are combined with programmable electronics. Such control systems are disclosed for instance in the European Patent Specifications EP 0 079843, JEP 0 068139 or EP 8 0105440.4. These systems comprise combinations of magnetic and mechanical control elements in which the respective mechanical part must act as memory and amplifier and contains always one or a plurality of control cams. In common among the aforementioned control systems is that they are located outside of the center of rotation of the coupling apparatus proper, that they include correspondingly large elements having relatively long distances of function or operation respectively, which generate large acceleration and deceleration forces in case of high rotational speeds of the machines; such augments in turn their wear and noise generation. Furthermore, the outer dimensions of these constructions which are due to their specific kind of operations are quite voluminous such that often disassembling difficulties arise in connection with the weaving machine. In order to allow a simple elimination of weaving flaws a dobby loom should additionally be in a position to be rotated from any position backwards in correspondence with the program, a task which can be accomplished with the aforementioned systems partly only by exertion of considerable efforts or then not at all.
SUMMARY OF THE INVENTION
It is, therefore, a general object of the invention to provide a control system for a coupling apparatus, specifically of a rotary dobby loom, which avoids the aforementioned drawbacks and allows accordingly high operational speeds and is independent from the sense of rotation and lends itself to a compact design.
A further object is to provide a control system for a coupling apparatus in which the operating means and at least parts of the control means for each dog are located inside the drive shaft.
According to the invention the stationary control system is located inside of the drive shaft, i.e. in the center of the coupling apparatus and preferably comprises one solenoid for each connecting rod having an armature which is combined with a spring biassed control element, which control element can influence directly the radially movable push rods during the stoppage phase of the hollow shaft and thus give the dog the control signal according to the pattern in that this dog is controlled into one of its two possible end positions. The solenoid is subjected to electrical current and excited or not excited, in a synchronized sequence by an electronically operating pattern control apparatus. This electronic pattern control apparatus forms no part of the invention and will, therefore, not be described in detail.
Preferably, a hollow shaft rotates intermittently at an 180° in synchronism with the loom and at a short duration of stoppage around the stationary elements of the control system. This hollow shaft includes two recesses located opposite each other by 180°, and the dog engages under action of a spring force into these recesses except it is prevented therefrom in a manner according to the pattern by the corresponding push rod. One radially movable push rod belongs to each respective recess, and the object or function of this rod is to transmit the control position of the control element to the dog.
According to a preferred embodiment the dog is radially guided within the eccentric hoop and is subject to a spring force directed radially towards the center of rotation. If the control system is currentless, i.e. not excited, the spring of the control element, having a larger force than the one within the dog, urges the push rod towards the dog and urges the latter to disengage and move out of the recess of the hollow shaft and to simultaneously engage the recess of the connecting rod which embraces the eccentric hoop. If the hollow shaft continues its rotation after the stoppage phase the eccentric hoop remains together with the dog and the connecting rod in the rest position. Conclusively, the element which is coupled to the connecting rod, e.g. the heald of a weaving machine or loom remains in a rest position, e.g. in the bottom shed position. This condition changes as soon as the solenoid gets excited in the manner according to the pattern and attracts the armature and thus the control element; accordingly, the dog can engage into the recess in the hollow shaft under the influence of the spring force, whereupon the push rod at this side is dislocated in the direction towards the center of rotation while the opposite push rod is pushed into the empty recess of the hollow shaft.
If the hollow shaft continues its rotation after the stoppage phase the eccentric hoop will be taken along, i.e. rotated by the engaged dog and the connecting rod pivots from one end position into the other, together with the heald frame coupled thereto (upper shed position). After the hollow shaft has rotated 180° the next following control command will be initiated. If now the heald has to move in a manner according to the pattern into its bottom shed position for the next following weft insertion the solenoid remains unexcited and the dog remains in the recess of the hollow shaft such that accordingly the eccentric hoop is rotated along and the connecting rod returns into its original initial position. At the end of the 180° rotation of the hollow shaft the control element, which is subject to a higher spring force than the dog urges the latter by means of the push rod radially outwards into the recess of the connecting rod. The heald is again in its bottom shed position.
If the heald must remain in accordance with the pattern, in the upper shed position the solenoid is excited and accordingly attracts the armature and the control element. The control element urges the push rod radially against the dog and the latter out of engagement with the recess in the hollow shaft and into the recess in the connecting rod. If the hollow shaft continues its rotation after its stoppage phase the eccentric hoop remains together with the connecting rod in this position and the heald remains in its upper shed position. In accordance with the pattern, the dog will again engage the recess in the hollow shaft if the solenoid remains unexcited during the control phase.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 illustrates schematically a control system including a coupling apparatus of a rotating dobby loom in the stoppage position of the hollow shaft, in which the solenoid is deenergized and the coupling apparatus is in the bottom shed position of the heald frame;
FIG. 2 illustrates the control system of FIG. 1, in which the solenoid is energized and accordingly its armature attracted and the dog of the coupling apparatus is engaged in the recess of the hollow shaft;
FIG. 3 illustrates the hollow shaft with the dog in its engaged position, after a rotation of 90° and deenergized solenoid;
FIG. 4 illustrates the control system and coupling apparatus after a rotation of the hollow shaft of 180° relative to FIG. 1, in the upper shed position of the heald, solenoid deenergized and dog engaged in the recess of the hollow shaft;
FIG. 5 illustrates the same position as shown in FIG. 4, however with energized solenoid and attracted armature and dog engaged in the recess of the connecting rod;
FIG. 6 is a phase diagram of the control system and coupling apparatus;
FIG. 7 illustrates a horizontal section through the control system and coupling apparatus of FIG. 2;
FIG. 8 illustrates the actuating of the control elements by elements located at the face side of the supporting axis, such as solenoid, hydraulic and pneumatic cylinders, mechanical elements;
FIG. 9 is a section through line A--A of FIG. 8;
FIG. 10 is a section of a bipartite axis, including solenoid;
FIG. 11 is a partial section through line B--B of FIG. 10;
FIG. 12 is a section through a bipartite axis similar to FIG. 10;
FIG. 13 is a side view of a part of the structure shown in FIG. 12;
FIG. 14 illustrates a hollow shaft with recesses which are not continuous in axial direction;
FIG. 15 illustrates a section through the axis and a fluid actuated control element; and
FIG. 16 is a longitudinal section through the dobby loom including the heald control elements.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The control system comprises a solenoid 2 mounted in a stationary axis 1, 1' of which the armature 3 is combined with the control element 4 which is acted upon by the spring 5 and urged radially against the push rod 6. An intermittingly rotating drive shaft in the form of a hollow shaft 7 which comes to a short standstill after each half rotation of 180° includes two recesses 8, 8' located opposite one another into which the dog 9 can engage whereby a push rod 6, 6' is located in each recess. The dog is guided radially in the eccentric hoop 10 which in turn serves as a bearing for a connecting rod 11 while the second bearing area 12 of the connecting rod 11 is coupled to the shaft or heald frame 14, respectively via a compound lever arrangement 13, 13' journaled in a fixed bearing A.
The very simple operation of the control system described herein is as follows:
FIG. 1 illustrates the stoppage phase of the hollow shaft 7 which is represented in the graph of FIG. 6 by the line I, time vector "0". The solenoid 2 is currentless, not energized and the control element 4 having a head 4' urges the push rod 6 by means of the spring force F 1 of the spring 5 towards the dog 9 which is subjected to the spring force F 2 of spring 15 (F 1 >F 2 ) thus urging the dog 9 radially outwardly into the recess 16 in the connecting rod 11. The control element 4 is guided at both its ends in bearings 17, 17' to thereby assure an easy axial displacement thereof. Both ends of the control element are designed as ram heads 4' and during the control phase contact the push rods 6, 6'.
The position of the connecting rod which is illustrated in FIG. 1 corresponds to an end position of the heald coupled thereto, for instance to the bottom shed position of FIG. 5, line II.
If the hollow shaft 7 starts to rotate the eccentric hoop 10 remains stationary because it is held by the dog 9 engaging into the recess 16 of the connecting rod 11. Before the push rod 6 completely leaves the action area of the dog 9, the outer diameter of the hollow shaft will prevent a radial displacing of the dog 9 towards the center, such that during the semi rotation of the hollow shaft, in FIG. 6 in the area of the time vector "0 to A" the heald remains in its bottom shed position. Towards the end of the 180° rotation the recess 8 moves with the push rod 6 into the area of the stationary dog 9. The push rod 6' slides on the head 4" and prevents the dog when located oppositely of the recess 8' from engaging thereinto. If a further rotation of the hollow shaft 7 occurs after the stoppage phase without the solenoid 2 being energized the operational procedure described is repeated.
FIG. 2 illustrates, in FIG. 6 time vector "A", the control system during the stoppage phase of the hollow shaft 7 and the control command n according to the pattern by the solenoid 2 being energized and accordingly attracted armature 3 including control element 4. The spring 15 inside of the dog 9 urges latter into the recess 8 of the hollow shaft because the push rod 6 can follow the head 4'. The push rod 6' is pushed by the head 4" of the control element 4 into the free recess 8' of the hollow shaft.
Due to the engagement into the recess 8 the dog is form-locked to the hollow shaft while the opposite end 8 of the dog has moved away out of the range of action of the recess 16 in the connecting rod 11.
After the stoppage phase "A" the semi-rotation of the hollow shaft begins which takes the eccentric hoop 10 along to rotate therewith by means of the engaged dog 9.
FIG. 3 illustrates the position of the coupling system after a 90° rotation of the hollow shaft, in FIG. 6 time vector "B".
From FIG. 6 it can be seen that after the beginning of the rotation of the hollow shaft (inclined segments of line I) the solenoid 2 is switched to a deenergized condition and the control element 4 is pushed by the spring 5 radially into its outer position.
At the end of the 180° rotation of the hollow shaft, in FIG. 6 time vector "C", the heald 14 is in the upper shed position. During the stoppage phase of the hollow shaft the new control command according to the pattern, identified in FIG. 6 by n+1 is applied on the solenoid.
If no energizing of the solenoid occurs the dog remains engaged in the recess 8 of the hollow shaft (FIG. 4) and due to the subsequent rotational movement of the hollow shaft the heald is moved into the bottom shed position.
When the push rod 6 closely approaches head 4' of the control element, in FIG. 6 time vector "D", the solenoid 2 is energized by the control command N (FIG. 6) such that the push rod 6 is not in contact with the head 4' until the hollow shaft is in its rest position. Now the new pattern conform control command is applied on the solenoid 2, in FIG. 6 time vector "E".
If the heald 14 has to remain in the bottom shed position (FIG. 1) the solenoid 2 is currentless and the control element 4 urges the push rod 6 due to the action of spring 5 against the dog 9 and the latter is pushed out of the area of action of the recess 8 of the hollow shaft and engages into the recess 16 of the connecting rod 11 such as illustrated in FIG. 1.
If the heald must be brought again into the upper shed position the solenoid 2 remains energized during the complete time span from "D" to "F" (FIG. 6), this means that the dog 9 remains engaged in the recess 8 of the hollow shaft and, therefore, does not make an unnecessary radial control movement.
If the heald must remain in the upper shed position during more than one weft insertion of the weaving machine, corresponding to time vector "C", FIG. 6, the solenoid 2 is energized by the control command n+1 such that the control element 4 urges by means of its head 4" the push rod 6 radially against the dog 9 and pushes the latter into the recess 16' of the connecting rod 11, following which the dog 9 is moved out of the range of action of the recess 8 of the hollow shaft (FIG. 5). After the stoppage position the hollow shaft can continue its rotating while the eccentric hoop 10 is coupled form-locked to the connecting rod 11 and the heald remains in the upper shed position.
The graph of FIG. 6 shows that prior to phase n (movement of the heald for weft insertion n) the control command n-2 is applied onto the solenoid 2; prior to phase n+1 the control command n-1, etc. This sequence of control commands follows in that a push rod 6, 6' will never strike the head 4', 4" of the control element 4 shortly prior to reaching the stoppage phase of the hollow shaft.
The control apparatus described herein and operating in accordance with the graph of FIG. 6 has the considerable advantage that the coupling system operates in a correct weft insertion sequence, i.e. that the dobby loom can be rotated from any position forwards and backwards and that the program according to the pattern can be immediately converted to the correct movement of the heald. This is an important precondition for a simple operation of the machine, specifically during the pick finding operation.
In case of a misinformation, that is if phase n-2 is missing, for instance from the electronic control or upon a program change, the push rod 6, 6' could strike shortly prior to the stoppage phase of the hollow shaft 7 onto the head 4', 4" of the control element 4. Due to the corresponding design of the shape of the push rod 6, 6' and of the head 4', 4" the control element 4 is pushed against the spring 5 and, as soon as the dog 9 has reached the recess 16, 16' in the connecting rod 11, it will be pushed by the spring 5 into this arresting position (bottom shed position of the heald).
FIG. 7 illustrates a horizontal section of the control and coupling apparatus shown in FIG. 2.
Shown in FIGS. 8 and 9 is the manner in which the control elements 44 can be possibly operated axially from outside of the axis 1, 1'. The control elements 44 are guided radially in the axis half 1 and include for instance a groove 45 extending obliquely relative to their direction of movement, and a connecting rod 47 engages with its cams 46 into this groove 45, such that upon an axial movement of these connecting rods 47 due to solenoids 48, hydraulic or pneumatic cylinders 49 or mechanically, e.g. by cams 50 the control elements 44 are moved radially in a manner according to the pattern.
A possible arrangement and mounting of the solenoids is illustrated in FIGS. 10 and 11. Axially extending hollow spaces 60, 60' are provided in both halves 1, 1' of the axis and the electric circuitry 61 for the solenoids 2 are located in these halves. Furthermore, a cooling medium such as e.g. air may flow through the hollow spaces 60, 60'.
Regarding the assembling and maintenance of the control apparatus it is of advantage to have the axis designed such to have two axial halves 1 and 1'. FIGS. 12 and 13 illustrate one possibility of holding the halves 1, 1' together by means of screw bolts 62.
A design of the hollow shaft 70 in accordance with FIG. 14 is advantageous. The recesses for the dogs are shaped as pockets 71 and 71' in the hollow shaft 70 such that a continuous bearing surface 72 is provided for the bearing points between the hollow shaft 70 and the eccentric hoop, respectively.
FIG. 15 illustrates the mounting of fluid actuated control elements. The control element 74 which is designed in form of a piston 76 is located within the axis 73.
At the unidirectionally acting piston 76 the spring 5 urges the control element 74 into a radial end position. The feed lines 75 can be located in the free space between the axis 73 and the hollow shaft.
FIG. 16 illustrates a section through a simple embodiment of a construction according to the invention, embodying particularly the hollow shaft 7 and the stationary axis or support 1. The easy assembling and maintenance attributes of the invention is that the axis 1 is supported in the simplest manner in the hollow shaft 7 and may be disassembled and assembled in the form of a complete unit.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims.
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The control system of a coupling apparatus of a dobby loom includes a hollow drive shaft, at least one eccentric hoop supported thereupon and a connecting rod arranged therearound for a controlled drive of an element. A dog is supported radially displaceable in the eccentric hoop and may be brought in a controlled manner via corresponding actuating means into engagement either into one of two recesses of the connecting rod or in one of two recesses of the drive shaft. For structural simplicity, the actuating means and the direct control means for the dog are located within the drive shaft, i.e. in the center of roation of the coupling.
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BACKGROUND OF THE INVENTION
The present invention is related to a foldable bearing structure for moulding outer surfaces of vertical walls and their continuous or partial perimetric overhangs, in the shape of balconies and such like, provided with planes adapted to receive modulated sheets which, apart from being resistant, are capable of being provided with embossments, channels, etc. constituting utilitarian decorations, and, at the edges, sheets constituting sides of columns and bottoms of necks between the walls and the overhangs.
Removable structures for this purpose are known, but they are, as a rule, heavy, costly and difficult to handle in order to be brought to and removed from construction sites as well as to be mounted thereon.
The essence of the present invention resides in that the structure in question is light, its cost is relatively much lower than that of the known embodiments performing a similar task, and its weight does not require, as in the prior structures, elevator cranes or special transportation trucks, but it may be carried by conventional general purpose trucks and loaded onto or removed from the same at the site by a few workmen if trucks are used which do not carry their own loading and unloading equipment.
At the ends of its vertical wings this novel structure carries sheets constituting columns in such a way as to complete the inner moulds used jointly with these structures, and, moreover, it includes a rigid portal at the center of the span between the walls. In this way they bar efficiently the wings of the inner moulds and complement them.
An important feature of the structures in accordance with the present invention is characterized in that they are universal, i.e. they are capable of forming protruding angles (or corners) as well as inner angles, by removing the inner supplement whenever necessary. Likewise, they are capable of forming uninterrupted series where the project requires such constructions.
Another important feature is that they can be hoisted up onto and lowered from upper floors with the aid of conventional means, manual or motorized equipment, which exists at every site in order to hoist up or lower materials as, for instance, doors, windows and such like, and to pass through apertures practically of the same size as the minimum required for passing through the doors and windows.
An exemplary embodiment of the bearing structure for outer moulding surfaces according to the invention, includes a rigid central portal constituted by a main post, to the ends of which are fixed, on one and the same side, horizontal, coplanar upper and lower beams having their free ends secured diagonal stays at a point intermediate the main post. Two side frames are hinged by means of their vertical sides one on either side of the main post, to the horizontal sides of which frames are joined a plurality of removable secondary portals, similar to the rigid central portal and adapted for sustaining each an upper rectangle hinged by means of their smaller sides to said upper beam. A right-angled triangle is joined to each of the lower horizontal sides of the side frames, by means of their larger legs, while the smaller leg is adapted for nesting in channels provided in the said lower beam.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the nature of this invention and the manner in which the same can be put into practice, a preferred embodiment of same will now be given, with the aid of the appended drawings. It is to be understood, of course, that the said preferred embodiment is given merely by way of example and does not by any means limit the scope of the invention as defined in the foregoing paragraph.
In the appended drawings, where corresponding reference to equal parts:
FIG. 1 shows, in perspective, the structure according to this invention, folded and seen from the end which is closed by means of a hook;
FIG. 2 shows, in perspective, the same structure, but unfolded and seen from the side where the sheets constituting the moulding surfaces will be applied;
FIG. 3 shows, in perspective, the same embodiment as FIG. 2, but seen from the opposite end;
FIG. 4 shows the same embodiment as FIG. 3, but with the structure in its folding step (that of the secondary portals);
FIG. 5 shows the folding of the upper rectangles and the lower triangles;
FIG. 6 shows the folding of the side frames;
FIG. 7 shows the folded structure in a side view; and
FIG. 8 shows the folded structure seen from the side opposite the one showed in FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
As may be seen from the drawings, especially from FIG. 7, the structure according to this invention includes a rigid central portal formed by a vertical post 1, an upper beam 2 and a lower beam 3 which are horizontal and secured to the post 1 by means of upper and lower diagonal stays 4' and 4", respectively, the lower stay 4' being fixed between the post 1 and the lower beam 3. The upper stay 4 is fixed between the main post 1 and upper beam 2. Hinged to the post 1 there are frames comprised by horizontal sides 7' and vertical sides 7". Hinged to the upper beam 2 there are rectangular structures comprised by the smaller side 5' and a larger side 5". The frame of the sides 7' and 7" are associated with cross members 17 and similarly as the rectangles of sides 5' and 5" they define planes and are adapted for receiving plates having moulding surfaces (not shown).
Hinged to the frames compared by the sides 7'-7" there are secondary portals constituted by posts 11, upper beams 12, lower beams 13 and diagonal stays 14'-14", similar to the rigid portal defined by the members 1-2-3 but differing from the same in that, apart from its thickness, the upper beams 12 are jointed to the upper end of post 11 and adapted for coupling (FIG. 3) by means of a bolt 24, to the upper diagonal stay 14'. Furthermore, the diagonal stays 14' are secured to the posts 11 by reinforcement bars 16. Hinged to the lower sides 7' by means of a larger leg, there is a right-angled triangular structure having a hypothenuse 8, the smaller leg 9 of which (FIG. 5) is adapted for entering into channel 10 provided on the upper face of the lower beam 3. This lower beam 3 and the lower sides 7' of the lateral frames carry, on its lower portion, casters 15 allowing the structure to roll when the same is folded as shown in FIGS. 1, 7 and 8.
The operation is as follows: The structure according to this invention, when folded (FIGS. 1, 7 and 8), may be loaded onto conventional, general purpose trucks and moved to the site and from there, rolling on the casters 15, to its final location. There the hook (see FIG. 2) is unhooked (FIG. 1) and the frames are spread out from the sides 7'-7", as shown in FIG. 6, to their coplanar position, as seen in FIG. 5, where they are secured by folding back the hypothenuse member 8 and the smaller leg 9 as far as to lodge the latter in the corresponding channel 10 of the lower beam 3 of the main portal. Subsequently, the rectangles of sides 5'-5" are put into a horizontal position, as shown in FIG. 5 and, once they are horizontal, as shown in FIG. 4, the secondary portals are folded back so as to locate the horizontal beams 12-13 and their corresponding diagonal stays 14'-14" in planes perpendicular to the sides 7'-7", whereupon, by means of a bolt 24, the connection 12-14' is made. The upper horizontal beams 12 serve then as a bearing for the frames of sides 5'-5", and the beams 13 rest on the hypothenuse member 8. The structure may be provided, at the planes defined by the frames 7'-7" and the rectangles 5'-5", with the sheets constituting the moulding surfaces, whereupon concrete may be poured.
In order to dismantle the structure, these operations are carried out in reverse sequence, whereby the folded structure of FIGS. 1, 7 and 8 is obtained which may be moved to any desirable location.
It is obvious that many modifications of detail may be made in the embodiment as described, such as: providing the sides 5" with bevels, to which are fixed sheets 19' defining the necks between the overhang and the moulded wall and which are complemented by means of sheets 19" applied to the sides 7' of frames 7'-7" as may be appreciated in FIGS. 1, 2 and 8; applying a sloping sheet 20 to the upper end of post 1 (FIGS. 2 and 8); and improving the coupling of the lower beam 3 with the frames of sides 7'-7" by means of tie rods 21 (FIGS. 4, 5, 6 and 7), on end of which is jointed to the lower side 7', while the other one is jointed to a bolt of the usual type sliding in a channel (not visible), located on the lower side of the lower beam 3, however, all such modifications, as well as others, fall within the scope of this invention as defined in the following claims.
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A foldable bearing structure for moulding outer surfaces comprises a main post to which are hinged upper and lower beams supported by diagonal elements, with side frames hinged by means of their vertical sides to the main post. The construction is light-weight and its cost is relatively low.
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TECHNICAL FIELD
The invention relates to a system for reproducing information from an optically readable record carrier on which information is recorded in the form of an encoded series of digital signal samples which are recovered by decoding after read-out.
The invention also relates to an apparatus for use in said system and a record carrier for use in said system.
Such a system, apparatus and record carrier is described in Phillips Technical review, Vol. 40, 1982 No. 6. The entire issue, is incorporated herewith by reference. Such apparatuses and record carriers are commercially available under the name of Compact Disc Digital Audio System and are used inter alia for reproducing audio information which is recorded on the optically readable record carrier in digital form by means of an EFM code. By means of these known players record carriers containing one hour of music can be played. The reproduction quality is excellent with respect to the linearity, bandwidth, dynamic range, and signal-to-noise ratio. However, for other purposes these properties may be of subordinate importance. An example of this is the reproduction of talking books for the blind. This requires a substantially smaller bandwidth and stereo reproduction is not necessary. Another example is functional music (background music) where the requirements imposed on the bandwidth and signal-to-noise ratio are less stringent than in the case of hi-fi reproduction. However, for these latter uses long playing time is very desirable. For reasons of economy and compatibility it is also desirable to obtain such a long playing time without significantly modifying the existing Compact Disc Digital Audio player and without modifying the standard EFM code. Solutions such as compression-expansion techniques and time-multiplexing techniques with repeated scanning of the same track turn demand significant modification of the player and it is often impossible to accommodate the synchronizing signals required for such uses within the optimized and standardized EFM code.
SUMMARY OF THE INVENTION
It is the object of the invention to provide a system of the type specified in the opening paragraph as well as an apparatus and a record carrier for use in this system, which yield a longer playing time by limiting the bandwidth without departing from the standard EFM coding used in the Compact Disc Digital Audio System and requiring only a slight modification of the known Compact Disc Digital Audio players.
According to the invention the system is characterized in that N information channels are multiplexed on the record carrier so that each time N consecutive samples are associated with N different information channels and the N information channels can be reproduced one by one by playing the entire record carrier N times, each time under selection of the samples associated with the channel.
In the system according to the present invention the record carrier is played in the same way as in the known players. Modification of the known player comprises a demultiplexer on the digital output and a digital-to-analog converter operated at a lower sampling frequency. The decoding and driving control means need not be modified.
With respect to synchronization of the sample selection, the system according to the present invention may be characterized in that each time at least one bit of the digital samples is used as a synchronizing bit so that during consecutive read-out of the samples the sequence of the bits results in a synchronizing signal which is used for synchronizing the selection of the samples associated with the channel to be reproduced instantaneously.
Thus, by use of one or a few bits of the standard sample (16 bits) for synchronization purposes a synchronizing signal is obtained without modifications to the EFM coding. The fact that this reduces the number of bits available for the audio signal merely leads to a reduction in signal-to-noise ratio which is permissible for the present purpose. Indeed, 14 to 15 bits are sufficient for satisfactory reproduction of speech or functional music.
The preferred embodiment may be characterized further in that the least significant bit of the samples is selected as a synchronizing bit.
The advantage of this embodiment is that a 16-bit analog-to-digital converter may be used without extraction of the synchronizing bit. The digital-to-analog converter supplies this synchronizing bit as a d.c. signal because this bit does not vary within the series of selected samples (but it does vary within the sequence of samples read!).
The apparatus for use in the system in accordance with the invention, comprises a read device, a decoding circuit, and a read-control circuit. The apparatus further comprises selection means for selecting a specific sample from every N samples being reproduced and control means which are constructed to repeatedly play the record carrier and, after every scan, to advance a channel counter which controls the selection means so that the samples associated with the relevant channel are selected.
In another embodiment this apparatus comprises means for extracting synchronizing bits from the decoded signal samples for synchronizing the selection means.
Alternatively, in this preferred embodiment of the invention, in which the decoding circuit is constructed to supply two digital signal samples at the same time, the selection means comprise first switching means for selecting one of the two simultaneously supplied signal samples as a function of the count of the channel counter, and second switching means for selecting a specific sample from every 1/2 N samples reproduced via the first switching means as a function of the count of the channel counter, N being an even integer.
In the known apparatus the two simultaneously supplied samples are two stereo signal samples. By dispensing with stereo reproduction, in accordance with the present invention, the playing time can be extended additionally by a factor of two.
The preferred embodiment provides a control for presetting the channel counter. This enables the user to start reproduction at any desired point, the starting point within the playing operation is set by the controls which are selectable by controls already present in the known players.
The record carrier for use in the system in accordance with the invention comprises N information channels which are multiplexed on the record carrier so that they can be reproduced consecutively by repeatedly playing the record carrier under selection of the signal samples associated with the channel to be reproduced.
The invention will now be described in more detail by way of example, with reference to the drawings, in which
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram illustrating the principle of the known Compact-Disc-Digital-Audio system,
FIG. 2 is a table to explain the principle underlying the invention,
FIG. 3 is a block diagram of a system as shown in FIG. 1 but modified in accordance with the invention, and
FIG. 4 shows some signal waveforms to illustrate the operation of the system shown in FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows schematically the construction of a "Compact Disc Digital Audio" player in so far as it is relevant to the present invention. The player comprises a drive motor 4 for rotating an optical record carrier 3. This record carrier 3 is read by means of a laser beam 2. The reflected laser beam is detected by a detector 1 which converts the amount of light received into an electric signal which is applied to a decoding circuit 5. The radial scanning position can be controlled by a radial drive motor 13, shown schematically. The decoding circuit comprises a demodulator 6 for demodulating the EFM-coded signal supplied by the detector 1. This demodulator 6 extracts inter alia a subcode from the signal, which subcode may contain information about the nature of the recorded signal, for example the title of the piece of music, address information such as the sequence number of the piece of music, and time information such as the elapsed playing time, the total playing time and the playing time per number. This information appears on an output 14 of the decoder circuit 5. The signal, which has been demodulated by the demodulator 6, is applied to an error-correction circuit 7 and subsequently, to a circuit 8 which re-arranges the signals and rejects incorrect audio samples or replaces them by samples obtained by interpolation. This circuit 8 supplies the audio samples as 16-bit parallel digital words to the outputs 9 and 10, each corresponding to one of the two stereo channels L and R. These stereo samples appear with a frequency of 44.1 kHz. Further, the circuit 5 comprises a clock generator 12 which supplies a clock signal with a sampling frequency of 44.1 kHz to the circuits 7 and 8 and to an output 11. The two stereo samples on the outputs 9 and 10 are applied to analog audio outputs 19 and 20 via a digital filter 16 and digital-to-analog converters 17 and 18 which are clocked by said 44.1 KHz clock signal.
The player further comprises a control and display device 15 which controls inter alia the drive motors 4 and 13, which may be effected depending on the user's wishes and set by means of a control 21, such as the address of the passage to be reproduced.
By means of this known apparatus it is possible to play record carriers on which one hour of music is recorded. The reproduction quality as regards linearity, bandwidth, dynamic range, and signal-to-noise ratio are then excellent. However, for some purposes these properties are less important. An example of this is the reproduction of talking books for the blind. For this purpose a substantially smaller bandwidth is required and stereo reproduction is not necessary. Moreover, less stringent requirements are imposed on the signal-to-noise ratio. Another example is functional music (background music) where the bandwidth may be substantially smaller. However, for both uses a long playing time is required. It is also desirable that this be achieved without significantly modifying the existing Compact Disc Digital Audio Player and the standard EFM coding. Solutions such as compression-expansion techniques and time-multiplexing techniques with repeated scanning of the same track turn will lead to considerable modifications to the player and it is impossible to accommodate the synchronizing signals required for this purpose within the optimized and standardized EFM coding. A solution resides in the use of time-multiplexing, not with repeated playing of each track turn but with repeated playing of the entire disc. The audio samples (with a repetition frequency of 44.1 kHz) are divided into groups of N (for Example 5) samples. During the first scan of the disc, all the first samples of these groups are reproduced. During a second scan of the entire disc all the second samples are reproduced and so forth. This results in an increase in playing time by a factor of N and a bandwidth limitation by the same factor N. If stereo reproduction is not required, an additional extension of the playing time by a factor of two can be obtained by providing the two stereo channels with separate information and using them as mono channels. a playing time of ten hours with a bandwidth of 4 kHz is obtained for N=5. For the synchronization one (or even more) of the 16 bits may be sacrificed. Suitably, the least significant bit is chosen for this. By choosing this bit as a function of the sequence number of the revelant sample within the group of N samples, a synchronizing pattern is obtained. For example, the bit may be a logic one for the first sample of the group and zero for all the other samples. If the least significant bit is selected for this purpose this bit need not be extracted. The sample may yet be converted as a 16-bit word, the fact that the least significant bit does not contain audio information but clock information has no influence because this does change when each time the same sample within the group of N samples is selected but remains the same, at least for one hour, so that it is present in the analog signal in the form of a d.c. component. For the present purpose the fact that the audio-information 15 bits instead of 16 bits are available, is not objectionable.
By way of illustration, FIG. 2 shows schematically a series of stereo samples S 1 to S 16 . These stereo samples each comprise a 16-bit sample L for the left-hand stereo channel and a 16-bit sample R for the right-hand stereo channel. The bits b 1 to b 15 of each sample are available as information bits while bit 16 is the synchronizing bit and is a logic one for every first one of five samples.
If the stereo samples are not separated into two independent mono samples belonging to different channels, it is in principle adequate to select one synchronizing bit in only one of the two stereo channels.
This will be explained with reference to FIG. 3 which shows a Compact Disc Digital Audio player modified in conformity with the foregoing. In comparison with the player shown in FIG. 1, the digital filter 16 and the digital-to-analog converters 17 and 18 have been dispensed with. The digital audio outputs 9 and 10 are connected to a switch 24 by means of which one of the two stereo channels is selected and applied to a hold circuit 25 by means of which a specific sample out of each time one group of N is selected and transferred to a digital-to-analog converter 26, which then operates with a frequency of 44.1/N kHz. The resulting analog output signal is supplied to an output 28 via a low-pass filter 27 which has a cut-off frequency of 20/n kHz.
The hold circuit 25 comprises an input 45 to which a signal may be applied under command of which the hold circuit receives and holds the instantaneously appearing sample until the next command, and an output 29 on which the least-significant bit of all the words appears, i.e. the synchronizing signal. This hold signal is supplied by a counter 23, which counts the clock signal (44.1 kHz) appearing on output 11 and which is reset by the synchronizing signal, i.e. the least-significant bit of every first sample of every group of N bits. The count of the counter 23 then corresponds to the sequence number of the instantaneously appearing sample within the group of N samples. Via a set input 35 the counter 23 can be set so that the count defined by the signal on input 35 generates a hold signal for the hold circuit 25, so that always that sample of the group of N samples which within the group has a sequence number corresponding to the signal on input 35 is reproduced on output 28.
The signal on input 35 is supplied by a counter 32 which receives a count signal from the control and reproducing device 15 on its input 33 after completion of every scan of the disc, device 15 being constructed so that after this, the disc is scanned again from the beginning. Via the counter 23 the next sample is selected from the group of N samples. After N steps of the counter 32 the switch 24 is changed over. In the present example where N=5, this is effected in that by means of the AND-gate 30 the count 4 (=100), i.e. the fifth count, is decoded. After being suitably delayed by the gate 30 this decoded count is combined with the next counting pulse on input 33 in AND-gate 31, so that this AND-gate 31 produces a signal at the end of the fifth scan of the disc. This signal resets the counter 32 via its reset input R and sets the flip-flop 34, which switches the switch 24 from the left-hand channel to the right-hand channel.
FIG. 4 shows some signal waveforms to explain the operation of the apparatus shown in FIG. 3. The signal a is the counting signal on output 33 and comprises a pulse at the end of every scan of the disc, i.e. after every hour. The signal b is the output signal of the AND-gate 31 which resets the counter 32 and which changes-over the flip-flop 34. Signal c is the output signal of the flip-flop 34 which is representative of the state of the switch 24, and curve d represents the count of the counter 32.
By means of a control 22 the user can preset the counter 32 to select a desired scan of the series of 2 N scans and the starting position within the scan can be selected by the addressing means 21 which is also provided with the conventional player shown in FIG. 1.
Instead of manual setting of the control 21, it is alternatively possible to equip the player so that if the scan of the disc is interrupted the position of the channel counter 23 and the position within this scan are stored in a memory to enable starting at this position when the disc is played subsequently. This is possible because in the Compact Disc Digital Audio System the discs are provided with an "index" at the beginning of the disc. By use of this index the relevant disc is inter alia identified and the identification code is read by the control circuit. For this purpose the apparatus comprises a memory 40 which receives and stores a disc-identification code and the instantaneous position on the disc received from the control circuit 15 via a connection 44. Via the connection 44 the memory also receives the position of the channel counter 32. When the disc is to be played again this enables the control circuit 15 to be set via the connection 41 and the channel counter 32 via the connection 43 after read out of the disc-identification code, so that playing is continued at the same position where it was interrupted. Depending on the storage capacity the last playing positions of a plurality of discs may be stored.
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A compact-disc-digital-audio-system has bandwidth reduced in order to extend the playing time, for example for the reproduction of 10 hours of speech. This is achieved without significantly modifying the existing players and without affecting the standard EFM coding, by multiplexing a plurality of information channels in such a way that they can be reproduced consecutively by repeatedly playing the entire CD disc.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of co-pending application Ser. No. 10/678,562 which is a continuation-in-part of co-pending application Ser. No. 10/259,139, filed on Sep. 27, 2002, which is a continuation-in-part of co-pending application Ser. No. 10/123,389, filed on Apr. 16, 2002, all of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates to novel arylindenopyridines and arylindenopyrimidines and their therapeutic and prophylactic uses. Disorders treated and/or prevented using these compounds include neurodegenerative and movement disorders ameliorated by antagonizing Adenosine A2a receptors.
BACKGROUND OF THE INVENTION
[0000] Adenosine A2a Receptors
[0003] Adenosine is a purine nucleotide produced by all metabolically active cells within the body. Adenosine exerts its effects via four subtypes of cell-surface receptors (A1, A2a, A2b and A3), which belong to the G protein coupled receptor superfamily (Stiles, G. L. Journal of Biological Chemistry, 1992, 267, 6451). A1 and A3 couple to inhibitory G protein, while A2a and A2b couple to stimulatory G protein. A2a receptors are mainly found in the brain, both in neurons and glial cells (highest level in the striatum and nucleus accumbens, moderate to high level in olfactory tubercle, hypothalamus, and hippocampus etc. regions) (Rosin, D. L.; Robeva, A.; Woodard, R. L.; Guyenet, P. G.; Linden, J. Journal of Comparative Neurology, 1998, 401, 163).
[0004] In peripheral tissues, A2a receptors are found in platelets, neutrophils, vascular smooth muscle and endothelium (Gessi, S.; Varani, K.; Merighi, S.; Ongini, E.; Borea, P. A. British Journal of Pharmacology, 2000, 129, 2). The striatum is the main brain region for the regulation of motor activity, particularly through its innervation from dopaminergic neurons originating in the substantia nigra. The striatum is the major target of the dopaminergic neuron degeneration in patients with Parkinson's Disease (PD). Within the striatum, A2a receptors are co-localized with dopamine D2 receptors, suggesting an important site for the integration of adenosine and dopamine signaling in the brain (Fink, J. S.; Weaver, D. R.; Rivkees, S. A.; Peterfreund, R. A.; Pollack, A. E.; Adler, E. M.; Reppert, S. M. Brain Research Molecular Brain Research, 1992, 14, 186).
[0005] Neurochemical studies have shown that activation of A2a receptors reduces the binding affinity of D2 agonist to their receptors. This D2R and A2aR receptor-receptor interaction has been demonstrated in striatal membrane preparations of rats (Ferre, S.; von Euler, G.; Johansson, B.; Fredholm, B. B.; Fuxe, K. Proceedings of the National Academy of Sciences of the United States of America, 1991, 88, 7238) as well as in fibroblast cell lines after transfected with A2aR and D2R cDNAs (Salim, H.; Ferre, S.; Dalal, A.; Peterfreund, R. A.; Fuxe, K.; Vincent, J. D.; Lledo, P. M. Journal of Neurochemistry, 2000, 74, 432). In vivo, pharmacological blockade of A2a receptors using A2a antagonist leads to beneficial effects in dopaminergic neurotoxin MPTP(1-methyl-4-pheny-1,2,3,6-tetrahydropyridine)-induced PD in various species, including mice, rats, and monkeys (Ikeda, K.; Kurokawa, M.; Aoyama, S.; Kuwana, Y. Journal of Neurochemistry, 2002, 80, 262). Furthermore, A2a knockout mice with genetic blockade of A2a function have been found to be less sensitive to motor impairment and neurochemical changes when they were exposed to neurotoxin MPTP (Chen, J. F.; Xu, K.; Petzer, J. P.; Staal, R.; Xu, Y. H.; Beilstein, M.; Sonsalla, P. K.; Castagnoli, K.; Castagnoli, N., Jr.; Schwarzschild, M. A. Journal of Neuroscience, 2001, 21, RC143).
[0006] In humans, the adenosine receptor antagonist theophylline has been found to produce beneficial effects in PD patients (Mally, J.; Stone, T. W. Journal of the Neurological Sciences, 1995, 132, 129). Consistently, recent epidemiological study has shown that high caffeine consumption makes people less likely to develop PD (Ascherio, A.; Zhang, S. M.; Hernan, M. A.; Kawachi, I.; Colditz, G. A.; Speizer, F. E.; Willett, W. C. Annals of Neurology, 2001, 50, 56). In summary, adenosine A2a receptor blockers may provide a new class of antiparkinsonian agents (Impagnatiello, F.; Bastia, E.; Ongini, E.; Monopoli, A. Emerging Therapeutic Targets, 2000, 4, 635).
SUMMARY OF THE INVENTION
[0007] This invention provides a compound having the structure of Formula I or II
or a pharmaceutically acceptable salt thereof, wherein (a) R 1 is selected from the group consisting of
(i)-COR 5 , wherein R 5 is selected from H, optionally substituted C 1-8 straight or branched chain alkyl, optionally substituted aryl and optionally substituted arylalkyl;
wherein the substituents on the alkyl, aryl and arylalkyl group are selected from C 1-8 alkoxy, phenylacetyloxy, hydroxy, halogen, p-tosyloxy, mesyloxy, amino, cyano, carboalkoxy, or NR 7 R 8 wherein R 7 and R 8 are independently selected from the group consisting of hydrogen, C 1-8 straight or branched chain alkyl, C 3-7 cycloalkyl, benzyl, aryl, or heteroaryl or NR 7 R 8 taken together form a heterocycle or heteroaryl;
(ii) COOR 5 , wherein R 5 is as defined above; (ii) cyano; (iii) —CONR 9 R 10 wherein R 9 and R 10 are independently selected from H, C 1-8 straight or branched chain alkyl, C 3-7 cycloalkyl, trifluoromethyl, hydroxy, alkoxy, acyl, alkylcarbonyl, carboxyl, arylalkyl, aryl, heteroaryl and heterocyclyl;
wherein the alkyl, cycloalkyl, alkoxy, acyl, alkylcarbonyl, carboxyl, arylalkyl, aryl, heteroaryl and heterocyclyl groups may be substituted with carboxyl, alkyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, hydroxamic acid, sulfonamide, sulfonyl, hydroxy, thiol, amino, alkoxy or arylalkyl, or R 9 and R 10 taken together with the nitrogen to which they are attached form a heterocycle or heteroaryl group;
(v) optionally substituted C 1-8 straight or branched chain alkyl;
wherein the substituents on the alkyl, group are selected from C 1-8 alkoxy, phenylacetyloxy, hydroxy, halogen, p-tosyloxy, mesyloxy, amino, cyano, carboalkoxy, carboxyl, aryl, heterocyclyl, heteroaryl, sulfonyl, thiol, alkylthio, or NR 7 R 8 wherein R 7 and R 8 are as defined above;
(b) R 2 is selected from the group consisting of optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl and optionally substituted C 3-7 cycloalkyl, C 1-8 alkoxy, aryloxy, C 1-8 alkylsulfonyl, arylsulfonyl, arylthio, C 1-8 alkylthio, or —NR 24 R 25
wherein R 24 and R 25 are independently selected from H, C 1-8 straight or branched chain alkyl, arylalkyl, C 3-7 cycloalkyl, carboxyalkyl, aryl, heteroaryl, and heterocyclyl or R 24 and R 25 taken together with the nitrogen form a heteroaryl or heterocyclyl group,
(c) R 3 is from one to four groups independently selected from the group consisting of:
hydrogen, halo, C 1-8 straight or branched chain alkyl, arylalkyl, C 3-7 cycloalkyl, C 1-8 alkoxy, cyano, C 1-4 carboalkoxy, trifluoromethyl, C 1-8 alkylsulfonyl, halogen, nitro, hydroxy, trifluoromethoxy, C 1-8 carboxylate, aryl, heteroaryl, and heterocyclyl, —NR 11 R 12 ,
wherein R 11 and R 12 are independently selected from H, C 1-8 straight or branched chain alkyl, arylalkyl, C 3-7 cycloalkyl, carboxyalkyl, aryl, heteroaryl, and heterocyclyl or R 10 and R 11 taken together with the nitrogen form a heteroaryl or heterocyclyl group,
—NR 13 COR 14 ,
wherein R 13 is selected from hydrogen or alkyl and R 14 is selected from hydrogen, alkyl, substituted alkyl, C 1-3 alkoxyl, carboxyalkyl, aryl, arylalkyl, heteroaryl, heterocyclyl, R 15 R 16 N(CH 2 ) p —, or R 15 R 16 NCO(CH 2 ) p —, wherein R 15 and R 16 are independently selected from H, OH, alkyl, and alkoxy, and p is an integer from 1-6, wherein the alkyl group may be substituted with carboxyl, alkyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, hydroxamic acid, sulfonamide, sulfonyl, hydroxy, thiol, alkoxy or arylalkyl, or R 13 and R 14 taken together with the carbonyl form a carbonyl containing heterocyclyl group;
(d) R 4 is selected from the group consisting of hydrogen, C 1-6 straight or branched chain alkyl, benzyl
wherein the alkyl and benzyl groups are optionally substituted with one or more groups selected from C 3-7 cycloalkyl, C 1-8 alkoxy, cyano, C 1-4 carboalkoxy, trifluoromethyl, C 1-8 alkylsulfonyl, halogen, nitro, hydroxy, trifluoromethoxy, C 1-8 carboxylate, amino, NR 17 R 18 , aryl and heteroaryl, —OR 17 , and —NR 17 R 18 ,
wherein R 17 and R 18 are independently selected from hydrogen, and optionally substituted C 1-6 alkyl or aryl; and
(e) X is selected from C═S, C═O; CH 2 , CHOH, CHOR 19 ; or CHNR 2 OR 21 where R 19 , R 20 , and R 21 are selected from optionally substituted C 1-8 straight of branched chain alkyl, wherein the substituents on the alkyl group are selected from C 1-8 alkoxy, hydroxy, halogen, amino, cyano, or NR 22 R 23 wherein R 22 and R 23 are independently selected from the group consisting of hydrogen, C 1-8 straight or branched chain alkyl, C 3-7 cycloalkyl, benzyl, aryl, heteroaryl, or NR 22 R 23 taken together from a heterocycle or heteroaryl; with the proviso that in a compound of Formula II when R 1 is a cyano, then R 2 is not phenyl.
[0031] This invention also provides a pharmaceutical composition comprising the instant compound and a pharmaceutically acceptable carrier.
[0032] This invention further provides a method of treating a subject having a condition ameliorated by antagonizing Adenosine A2a receptors, which comprises administering to the subject a therapeutically effective dose of the instant pharmaceutical composition.
[0033] This invention further provides a method of preventing a disorder ameliorated by antagonizing Adenosine A2a receptors in a subject, comprising of administering to the subject a prophylactically effective dose of the compound of claim 1 either preceding or subsequent to an event anticipated to cause a disorder ameliorated by antagonizing Adenosine A2a receptors in the subject.
DETAILED DESCRIPTION OF THE INVENTION
[0034] Compounds of Formula I are potent small molecule antagonists of the Adenosine A2a receptors that have demonstrated potency for the antagonism of Adenosine A2a, A1, and A3 receptors.
[0035] Preferred embodiments for R 1 are COOR 5 wherein R 5 is an optionally substituted C 1-8 straight or branched chain alkyl. Preferably the alkyl chain is substituted with a dialkylamino group.
[0036] Preferred embodiments for R 2 are optionally substituted heteroaryl and optionally substituted aryl. Preferably, R 2 is an optionally substituted furan.
[0037] Preferred substituents for R 3 include hydrogen, halo, hydroxy, amino, trifluoromethyl, alkoxy, hydroxyalkyl chains, and aminoalkyl chains,
[0038] Preferred substituents for R 4 include NH 2 and alkylamino.
[0039] In a preferred embodiment, the compound is selected from the group of compounds shown in Tables 1 and 2 hereinafter.
[0040] More preferably, the compound is selected from the following compounds:
[0041] The compound of claim 1 , formula I, wherein R 4 is amino.
2-amino-4-furan-2-yl-indeno[1,2-d]pyrimidin-5-one
[0042]
2-amino-4-phenyl-indeno[1,2-d]pyrimidin-5-one
[0043]
2-amino-4-thiophen-2-yl-indeno[1,2-d]pyrimidin-5-one
[0044]
2-amino-4-(5-methyl-furan-2-yl)-indeno[1,2-d]pyrimidin-5-one
[0045]
2,6-diamino-4-fu ran-2-yl-indeno[1,2-d]pyrim idin-5-one
[0046]
9H-indeno[2,1-c]pyridine-4-carbonitrile, 3-amino-1-furan-2-yl-9-oxo-
[0047]
9H-indeno[2,1-c]pyridine-4-carboxylic acid, 3-amino-1-furan-2-yl-9-oxo-, 2-dimethylamino-ethyl ester
[0048]
9H-indeno[2,1-c]pyridine-4-carboxylic acid, 3-amino-1-phenyl-9-oxo-, 2-dimethylamino-ethyl ester
[0049]
9H-indeno[2,1-c]pyridine-4-carboxylic acid, 3-amino1-furan-2-yl-9-oxo-, (2-dimethylamino-1-methyl-ethyl)-amide
[0050]
9H-indeno[2,1-c]pyridine-4-carboxylic acid, 3-amino-1-furan-2-yl-9-oxo-, (2-dimethylamino-ethyl)-methyl-amide
[0051]
9H-indeno[2,1-c]pyridine-4-carboxylic acid, 3-amino-1-furan-2-yl-9-oxo-, 1-methyl-pyrrolidin-2-ylmethyl ester
[0052] The instant compounds can be isolated and used as free bases. They can also be isolated and used as pharmaceutically acceptable salts. Examples of such salts include hydrobromic, hydroiodic, hydrochloric, perchloric, sulfuric, maleic, fumaric, malic, tartaric, citric, benzoic, mandelic, methanesulfonic, hydroethanesulfonic, benzenesulfonic, oxalic, palmoic, 2-naphthalenesulfonic, p-toluenesulfonic, cyclohexanesulfamic and saccharic.
[0053] This invention also provides a pharmaceutical composition comprising the instant compound and a pharmaceutically acceptable carrier.
[0054] Pharmaceutically acceptable carriers are well known to those skilled in the art and include, but are not limited to, from about 0.01 to about 0.1 M and preferably 0.05 M phosphate buffer or 0.8% saline. Such pharmaceutically acceptable carriers can be aqueous or non-aqueous solutions, suspensions and emulsions. Examples of non-aqueous solvents are propylene glycol, polyethylene glycol, vegetable oils such as olive oil, and injectable organic esters such as ethyl oleate. Aqueous carriers include water, ethanol, alcoholic/aqueous solutions, glycerol, emulsions or suspensions, including saline and buffered media. Oral carriers can be elixirs, syrups, capsules, tablets and the like. The typical solid carrier is an inert substance such as lactose, starch, glucose, methyl-cellulose, magnesium stearate, dicalcium phosphate, mannitol and the like. Parenteral carriers include sodium chloride solution, Ringer's dextrose, dextrose and sodium chloride, lactated Ringer's and fixed oils. Intravenous carriers include fluid and nutrient replenishers, electrolyte replenishers such as those based on Ringer's dextrose and the like. Preservatives and other additives can also be present, such as, for example, antimicrobials, antioxidants, chelating agents, inert gases and the like. All carriers can be mixed as needed with disintegrants, diluents, granulating agents, lubricants, binders and the like using conventional techniques known in the art.
[0055] This invention further provides a method of treating a subject having a condition ameliorated by antagonizing Adenosine A2a receptors, which comprises administering to the subject a therapeutically effective dose of the instant pharmaceutical composition.
[0056] In one embodiment, the disorder is a neurodegenerative or movement disorder. Examples of disorders treatable by the instant pharmaceutical composition include, without limitation, Parkinson's Disease, Huntington's Disease, Multiple System Atrophy, Corticobasal Degeneration, Alzheimer's Disease, and Senile Dementia.
[0057] In one preferred embodiment, the disorder is Parkinson's disease.
[0058] As used herein, the term “subject” includes, without limitation, any animal or artificially modified animal having a disorder ameliorated by antagonizing adenosine A2a receptors. In a preferred embodiment, the subject is a human.
[0059] Administering the instant pharmaceutical composition can be effected or performed using any of the various methods known to those skilled in the art. The instant compounds can be administered, for example, intravenously, intramuscularly, orally and subcutaneously. In the preferred embodiment, the instant pharmaceutical composition is administered orally. Additionally, administration can comprise giving the subject a plurality of dosages over a suitable period of time. Such administration regimens can be determined according to routine methods.
[0060] As used herein, a “therapeutically effective dose” of a pharmaceutical composition is an amount sufficient to stop, reverse or reduce the progression of a disorder. A “prophylactically effective dose” of a pharmaceutical composition is an amount sufficient to prevent a disorder, i.e., eliminate, ameliorate and/or delay the disorder's onset. Methods are known in the art for determining therapeutically and prophylactically effective doses for the instant pharmaceutical composition. The effective dose for administering the pharmaceutical composition to a human, for example, can be determined mathematically from the results of animal studies.
[0061] In one embodiment, the therapeutically and/or prophylactically effective dose is a dose sufficient to deliver from about 0.001 mg/kg of body weight to about 200 mg/kg of body weight of the instant pharmaceutical composition. In another embodiment, the therapeutically and/or prophylactically effective dose is a dose sufficient to deliver from about 0.05 mg/kg of body weight to about 50 mg/kg of body weight. More specifically, in one embodiment, oral doses range from about 0.05 mg/kg to about 100 mg/kg daily. In another embodiment, oral doses range from about 0.05 mg/kg to about 50 mg/kg daily, and in a further embodiment, from about 0.05 mg/kg to about 20 mg/kg daily. In yet another embodiment, infusion doses range from about 1.0 μg/kg/min to about 10 mg/kg/min of inhibitor, admixed with a pharmaceutical carrier over a period ranging from about several minutes to about several days. In a further embodiment, for topical administration, the instant compound can be combined with a pharmaceutical carrier at a drug/carrier ratio of from about 0.001 to about 0.1.
[0000] Definitions and Nomenclature
[0062] Unless otherwise noted, under standard nomenclature used throughout this disclosure the terminal portion of the designated side chain is described first, followed by the adjacent functionality toward the point of attachment.
[0063] As used herein, the following chemical terms shall have the meanings as set forth in the following paragraphs: “independently”, when in reference to chemical substituents, shall mean that when more than one substituent exists, the substituents may be the same or different;
[0064] “Alkyl” shall mean straight, cyclic and branched-chain alkyl. Unless otherwise stated, the alkyl group will contain 1-20 carbon atoms. Unless otherwise stated, the alkyl group may be optionally substituted with one or more groups such as halogen, OH, CN, mercapto, nitro, amino, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxyl, C 1 -C 8 -alkylthio, C 1 -C 8 -alkyl-amino, di(C 1 -C 8 -alkyl)amino, (mono-, di-, tri-, and per-) halo-alkyl, formyl, carboxy, alkoxycarbonyl, C 1 -C 8 alkyl-CO—O—, C 1 -C 8 -alkyl-CO—NH—, carboxamide, hydroxamic acid, sulfonamide, sulfonyl, thiol, aryl, aryl(c 1 -C 8 )alkyl, heterocyclyl, and heteroaryl.
[0065] “Alkoxy” shall mean —O-alkyl and unless otherwise stated, it will have 1-8 carbon atoms.
[0066] The term “bioisostere” is defined as “groups or molecules which have chemical and physical properties producing broadly similar biological properties.” (Burger's Medicinal Chemistry and Drug Discovery, M. E. Wolff, ed. Fifth Edition, Vol. 1, 1995, Pg. 785).
[0067] “Halogen” shall mean fluorine, chlorine, bromine or iodine; “PH” or “Ph” shall mean phenyl; “Ac” shall mean acyl; “Bn” shall mean benzyl.
[0068] The term “acyl” as used herein, whether used alone or as part of a substituent group, means an organic radical having 2 to 6 carbon atoms (branched or straight chain) derived from an organic acid by removal of the hydroxyl group. The term “Ac” as used herein, whether used alone or as part of a substituent group, means acetyl.
[0069] “Aryl” or “Ar,” whether used alone or as part of a substituent group, is a carbocyclic aromatic radical including, but not limited to, phenyl, 1- or 2-naphthyl and the like. The carbocyclic aromatic radical may be substituted by independent replacement of 1 to 5 of the hydrogen atoms thereon with halogen, OH, CN, mercapto, nitro, amino, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxyl, C 1 -C 8 -alkylthio, C 1 -C 8 -alkyl-amino, di(C 1 -C 8 -alkyl)amino, (mono-, di-, tri-, and per-) halo-alkyl, formyl, carboxy, alkoxycarbonyl, C 1 -C 8 -alkyl-CO—O—, C 1 -C 8 -alkyl-CO—NH—, or carboxamide. Illustrative aryl radicals include, for example, phenyl, naphthyl, biphenyl, fluorophenyl, difluorophenyl, benzyl, benzoyloxyphenyl, carboethoxyphenyl, acetylphenyl, ethoxyphenyl, phenoxyphenyl, hydroxyphenyl, carboxyphenyl, trifluoromethylphenyl, methoxyethylphenyl, acetamidophenyl, tolyl, xylyl, dimethylcarbamylphenyl and the like. “Ph” or “PH” denotes phenyl.
[0070] Whether used alone or as part of a substituent group, “heteroaryl” refers to a cyclic, fully unsaturated radical having from five to ten ring atoms of which one ring atom is selected from S, O, and N; 0-2 ring atoms are additional heteroatoms independently selected from S, O, and N; and the remaining ring atoms are carbon. The radical may be joined to the rest of the molecule via any of the ring atoms. Exemplary heteroaryl groups include, for example, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrroyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, thiadiazolyl, triazolyl, triazinyl, oxadiazolyl, thienyl, furanyl, quinolinyl, isoquinolinyl, indolyl, isothiazolyl, 2-oxazepinyl, azepinyl, N-oxo-pyridyl, 1-dioxothienyl, benzothiazolyl, benzoxazolyl, benzothienyl, quinolinyl-N-oxide, benzimidazolyl, benzopyranyl, benzisothiazolyl, benzisoxazolyl, benzodiazinyl, benzofurazanyl, benzothiopyranyl, indazolyl, indolizinyl, benzofuryl, chromonyl, coumarinyl, cinnolinyl, quinoxalinyl, indazolyl, pyrrolopyridinyl, furopyridinyl (such as furo[2,3-c]pyridinyl, furo[3,2-b]pyridinyl, or furo[2,3-b]pyridinyl), imidazopyridinyl (such as imidazo[4,5-b]pyridinyl or imidazo[4,5-c]pyridinyl), naphthyridinyl, phthalazinyl, purinyl, pyridopyridyl, quinazolinyl, thienofuryl, thienopyridyl, thienothienyl, and furyl. The heteroaryl group may be substituted by independent replacement of 1 to 5 of the hydrogen atoms thereon with halogen, OH, CN, mercapto, nitro, amino, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxyl, C 1 -C 8 -alkylthio, C 1 -C 8 -alkyl-amino, di(C 1 -C 8 -alkyl)amino, (mono-, di-, tri-, and per-) halo-alkyl, formyl, carboxy, alkoxycarbonyl, C 1 -C 8 -alkyl-CO—O—, C 1 -C 8 -alkyl-CO—NH—, or carboxamide. Heteroaryl may be substituted with a mono-oxo to give for example a 4-oxo-1H-quinoline.
[0071] The terms “heterocycle,” “heterocyclic,” and “heterocyclo” refer to an optionally substituted, fully or partially saturated cyclic group which is, for example, a 4- to 7-membered monocyclic, 7- to 11-membered bicyclic, or 10- to 15-membered tricyclic ring system, which has at least one heteroatom in at least one carbon atom containing ring. Each ring of the heterocyclic group containing a heteroatom may have 1, 2, or 3 heteroatoms selected from nitrogen atoms, oxygen atoms, and sulfur atoms, where the nitrogen and sulfur heteroatoms may also optionally be oxidized. The nitrogen atoms may optionally be quaternized. The heterocyclic group may be attached at any heteroatom or carbon atom.
[0072] Exemplary monocyclic heterocyclic groups include pyrrolidinyl; oxetanyl; pyrazolinyl; imidazolinyl; imidazolidinyl; oxazolyl; oxazolidinyl; isoxazolinyl; thiazolidinyl; isothiazolidinyl; tetrahydrofuryl; piperidinyl; piperazinyl; 2-oxopiperazinyl; 2-oxopiperidinyl; 2-oxopyrrolidinyl; 4-piperidonyl; tetrahydropyranyl; tetrahydrothiopyranyl; tetrahydrothiopyranyl sulfone; morpholinyl; thiomorpholinyl; thiomorpholinyl sulfoxide; thiomorpholinyl sulfone; 1,3-dioxolane; dioxanyl; thietanyl; thiiranyl; and the like. Exemplary bicyclic heterocyclic groups include quinuclidinyl; tetrahydroisoquinolinyl; dihydroisoindolyl; dihydroquinazolinyl (such as 3,4-dihydro-4-oxo-quinazolinyl); dihydrobenzofuryl; dihydrobenzothienyl; dihydrobenzoth iopyranyl; dihydrobenzothiopyranyl sulfone; dihydrobenzopyranyl; indolinyl; isochromanyl; isoindolinyl; piperonyl; tetrahydroquinolinyl; and the like.
[0073] Substituted aryl, substituted heteroaryl, and substituted heterocycle may also be substituted with a second substituted-aryl, a second substituted-heteroaryl, or a second substituted-heterocycle to give, for example, a 4-pyrazol-1-yl-phenyl or 4-pyridin-2-yl-phenyl.
[0074] Designated numbers of carbon atoms (e.g., C 1-8 ) shall refer independently to the number of carbon atoms in an alkyl or cycloalkyl moiety or to the alkyl portion of a larger substituent in which alkyl appears as its prefix root.
[0075] Unless specified otherwise, it is intended that the definition of any substituent or variable at a particular location in a molecule be independent of its definitions elsewhere in that molecule. It is understood that substituents and substitution patterns on the compounds of this invention can be selected by one of ordinary skill in the art to provide compounds that are chemically stable and that can be readily synthesized by techniques known in the art as well as those methods set forth herein.
[0076] Where the compounds according to this invention have at least one stereogenic center, they may accordingly exist as enantiomers. Where the compounds possess two or more stereogenic centers, they may additionally exist as diastereomers. Furthermore, some of the crystalline forms for the compounds may exist as polymorphs and as such are intended to be included in the present invention. In addition, some of the compounds may form solvates with water (i.e., hydrates) or common organic solvents, and such solvates are also intended to be encompassed within the scope of this invention.
[0077] Some of the compounds of the present invention may have trans and cis isomers. In addition, where the processes for the preparation of the compounds according to the invention give rise to mixture of stereoisomers, these isomers may be separated by conventional techniques such as preparative chromatography. The compounds may be prepared as a single stereoisomer or in racemic form as a mixture of some possible stereoisomers. The non-racemic forms may be obtained by either synthesis or resolution. The compounds may, for example, be resolved into their components enantiomers by standard techniques, such as the formation of diastereomeric pairs by salt formation. The compounds may also be resolved by covalent linkage to a chiral auxiliary, followed by chromatographic separation and/or crystallographic separation, and removal of the chiral auxiliary. Alternatively, the compounds may be resolved using chiral chromatography.
[0078] This invention will be better understood by reference to the Experimental Details which follow, but those skilled in the art will readily appreciate that these are only illustrative of the invention as described more fully in the claims which follow thereafter. Additionally, throughout this application, various publications are cited. The disclosure of these publications is hereby incorporated by reference into this application to describe more fully the state of the art to which this invention pertains.
Experimental Details
[0000] I. General Synthetic Schemes
[0079] Representative compounds of the present invention can be synthesized in accordance with the general synthetic methods described below and illustrated in the following general schemes. The products of some schemes can be used as intermediates to produce more than one of the instant compounds. The choice of intermediates to be used to produce subsequent compounds of the present invention is a matter of discretion that is well within the capabilities of those skilled in the art.
[0080] Procedures described in Schemes 1 to 7, wherein R 3a , R 3b , R 3c , and R 3c are independently any R 3 group, and R 1 , R 2 , R 3 , and R 4 are as described above, can be used to prepare compounds of the invention.
[0081] The substituted pyrimidines 1 can be prepared as shown in Scheme 1. The indanone or indandione 2 or the indene ester 3 can be condensed with an aldehyde to yield the substituted benzylidenes 4 (Bullington, J. L; Cameron, J. C.; Davis, J. E.; Dodd, J. H.; Harris, C. A.; Henry, J. R.; Pellegrino-Gensey, J. L.; Rupert, K. C.; Siekierka, J. J. Bioorg. Med. Chem. Lett. 1998, 8, 2489; Petrow, V.; Saper, J.; Sturgeon, B. J. Chem. Soc. 1949, 2134). This is then condensed with guanidine carbonate to form the indenopyrimidine 1.
[0082] Alternatively, the pyrimidine compounds can be prepared as shown in Scheme 2. Sulfone 6 can be prepared by oxidation of the thiol ether 5 and the desired amines 7 can be obtained by treatment of the sulfone with aromatic amines.
[0083] Pyrimidines with substituents on the fused aromatic ring could also be synthesized by the following procedure (Scheme 3). The synthesis starts with alkylation of furan with allyl bromide to provide 2-allylfuran. Diels-Alder reaction of 2-allylfuran with dimethylacetylene dicarboxylate followed by deoxygenation (Xing, Y. D.; Huang, N. Z. J. Org. Chem. 1982, 47, 140) provided the phthalate ester 8. The phthalate ester 8 then undergoes a Claisen condensation with ethyl acetate to give the styryl indanedione 9 after acidic workup (Buckle, D. R.; Morgan, N. J.; Ross, J. W.; Smith, H.; Spicer, B. A. J. Med. Chem. 1973, 16, 1334). The indanedione 9 is then converted to the dimethylketene dithioacetal 10 using carbon disulfide in the presence of KF. Addition of Grignard reagents to the dithioacetal 10 and subsequent reaction with guanidine provides the pyrimidines 11 as a mixture of isomers;
[0084] Dihydroxylation and oxidation give the aromatic aldehydes 13 that can be reductively aminated to provide amines 14. The other isomer can be treated in a similar manner.
[0085] 3-Dicyanovinylindan-1-one (15) (Scheme 5) was obtained using the published procedure (Bello, K. A.; Cheng, L.; Griffiths, J. J. Chem. Soc., Perkin Trans. II 1987, 815). Reaction of 3-dicyanovinylindan-1-one with an aldehyde in the presence of ammonium hydroxide produced dihydropyridines 16 (El-Taweel, F. M. A.; Sofan, M. A.; E.-Maati, T. M. A.; Elagamey, A. A. Boll. Chim. Farmac. 2001, 140, 306). These compounds were then oxidized to the corresponding pyridines 17 using chromium trioxide in refluxing acetic acid.
[0086] The ketone of pyridines 17 can be reduced to provide the benzylic alcohols 18. Alternatively, the nitrites can be hydrolyzed with sodium hydroxide to give the carboxylic acids 19 (Scheme 6).
[0087] The acids can then be converted to carboxylic esters 20 or amides 21 using a variety of methods. In general, the esters 20 are obtained by treatment with silver carbonate followed by an alkyl chloride or by coupling with diethylphosphoryl cyanide (DEPC) and the appropriate alcohol (Okawa, T.; Toda, M.; Eguchi, S.; Kakehi, A. Synthesis 1998, 1467). The amides 21 are obtained by coupling the carboxylic acid with the appropriate amine in the presence of DEPC or 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCl). Esters 20 can also be obtained by first reacting the carboxylic acids 19 with a dibromoalkane followed by displacement of the terminal bromide with an amine (Scheme 7).
II. Specific Compound Syntheses
[0088] Specific compounds which are representative of this invention can be prepared as per the following examples. No attempt has been made to optimize the yields obtained in these reactions. Based on the following, however, one skilled in the art would know how to increase yields through routine variations in reaction times, temperatures, solvents and/or reagents.
[0089] The products of certain syntheses can be used as intermediates to produce more than one of the instant compounds. In those cases, the choice of intermediates to be used to produce compounds of the present invention is a matter of discretion that is well within the capabilities of those skilled in the art.
EXAMPLE 1
Synthesis of Benzylidene 4
R 2 =2-furyl, R 3a =F, R 3b , R 3c , R 3c =H
[0090] A mixture of 3 (3.0 g, 11.69 mmol) and 2-furaldehyde (1.17 g, 12.17 mmol) in 75 mL of ethanol and 3 mL of concentrated hydrogen chloride was allowed to stir at reflux for 16 hours. The reaction was then cooled to room temperature, and the resulting precipitate was filtered off, washed with ethanol, diethyl ether, and air dried to afford 1.27 g (45%) of product.
EXAMPLE 2
Synthesis of Indenopyrimidine 1
R 2 =2-furyl, R 3a =F, R 3b , R 3c , R 3d =H
[0091] A mixture of 4 (0.5 g, 2.06 mmol), guanidine carbonate (0.93 g, 5.16 mmol), and 20.6 mL of 0.5 M sodium methoxide in methanol was stirred at reflux for 16 hours. The reaction mixture was cooled to room temperature, and diluted with water. The resulting precipitate was collected, washed with water, ethanol, diethyl ether, and then dried. Crude material was then purified over silica gel to afford 0.024 g (4%) of product. MS m/z282.0 (M+H).
EXAMPLE 3
Synthesis of 2-Amino-4-methanesulfonyl-indeno[1,2-d]pyrimidin-5-one
[0092] To a suspension of 5 (Augustin, M.; Groth, C.; Kristen, H.; Peseke, K.; Wiechmann, C. J. Prakt. Chem. 1979, 321, 205) (1.97 g, 8.10 mmol) in MeOH (150 mL) was added a solution of oxone (14.94 g, 24.3 mmol) in H 2 O (100 mL). The mixture was stirred at room temperature overnight then diluted with cold H 2 O (500 mL), made basic with K 2 CO 3 and filtered. The product was washed with water and ether to give 0.88 g (40%) of sulfone 6. MS m/z297.9 (M+Na).
EXAMPLE 4
Synthesis of Aminopyrimidine 7
R 2 =NHPh, R 3 =H
[0093] A mixture of sulfone 6 (0.20 g, 0.73 mmol) and aniline (0.20 g, 2.19 mmol) in N-methylpyrrolidinone (3.5 mL) was heated to 100° C. for 90 minutes. After cooling to room temperature, the mixture was diluted with EtOAc (100 mL), washed with brine (2×75 mL) and water (2×75 mL), and dried over Na 2 SO 4 . After filtration and concentration in vacuo, the residue was purified by column chromatography eluting with 0-50% EtOAc in hexane to yield 0.0883 g (42%) of product 7. MS m/z 289.0 (M+H).
EXAMPLE 5
Synthesis of Phthalate Ester 8
[0094] A 1.37 M hexanes solution of n-BuLi (53.6 mL, 73.4 mmol) was added to a cold, −78° C., THF solution (100 mL) of furan (5.3 mL, 73.4 mmol) and the reaction was then warmed to 0° C. After 1.25 h at 0° C. neat allyl bromide (7.9 mL, 91.8 mmol) was added in one portion. After 1 h at 0° C., saturated aqueous NH 4 Cl was added and the layers were separated. The aqueous phase was extracted with EtOAc and the combined organics were washed with water and brine, dried over Na 2 SO 4 , and concentrated to give 4.6 g (58%) of 2-allylfuran which was used without further purification.
[0095] The crude allyl furan (4.6 g, 42.6 mmol) and dimethylacetylene dicarboxylate (5.2 mL, 42.6 mmol) were heated to 90° C. in a sealed tube without solvent. After 6 h at 90° C. the material was cooled and purified by column chromatography eluting with 25% EtOAc in hexanes to give 5.8 g (54%) of the oxabicycle as a yellow oil. MS m/z 251 (M+H).
[0096] Tetrahydrofuran (60 mL) was added dropwise to neat TiCl 4 (16.5 mL, 150.8 mmol) at 0° C. A 1.0 M THF solution of LiAlH 4 (60.3 mL, 60.3 mmol) was added dropwise, changing the color of the suspension from yellow to a dark green or black suspension. Triethylamine (2.9 mL, 20.9 mmol) was added and the mixture was refluxed at 75-80° C. After 45 min, the solution was cooled to rt and a THF solution (23 mL) of the oxabicycle (5.8 g, 23.2 mmol) was added to the dark solution. After 2.5 h at rt, the solution was poured into a 20% aq. K 2 CO 3 solution (200 mL) and the resulting suspension was filtered. The precipitate was washed several times with CH 2 Cl 2 and the filtrate layers were separated. The aqueous phase was extracted with CH 2 Cl 2 and the combined organics were washed with water and brine, dried over Na 2 SO 4 , concentrated, and purified by column chromatography eluting with 25% EtOAc in hexanes to give 3.5 g (64%) of the phthalate ester 8 as a yellow oil. MS m/z 235 (M+H).
EXAMPLE 6
Synthesis of Indanedione 9
[0097] A 60% dispersion of sodium hydride in mineral oil (641 mg, 16.0 mmol) was added to an EtOAc solution (3.5 mL) of the phthalate ester 8 (2.5 g, 10.7 mmol), and the resulting slurry was refluxed. After 1 h the solution became viscous so an additional 7.5 mL of EtOAc was added. After 4 h at reflux the suspension was cooled to rt and filtered to give a yellow solid. This solid was added portionwise to a solution of HCl (25 mL water and 5 mL conc. HCl) at 80° C. The suspension was heated for an additional 30 min at 80° C., cooled to rt, and filtered to give 1.2 g (60%) of the indanedione 9 as a yellow solid. MS m/z 187 (M+H).
EXAMPLE 7
Synthesis of Dimethylketene Dithioacetal 10
[0098] Solid potassium fluoride (7.5 g, 129.1 mmol) was added to a 0° C. solution of indanedione 9 (1.2 g, 6.5 mmol) and CS 2 (0.47 mL, 7.8 mmol) in DMF (10 mL). The cold bath was removed and after 30 min neat iodomethane (1.00 mL, 16.3 mmol) was added. After 5 h at rt, the suspension was diluted with EtOAc and then washed with water and brine. The organic layer was dried over Na 2 SO 4 , concentrated, and purified by column chromatography eluting with 20% EtOAc in hexanes to give 1.4 g (75%) of the dimethylketene dithioacetal 10 as a yellow solid. MS m/z 291 (M+H).
EXAMPLE 8
Synthesis of Pyrimidine 11
R 2 =Ph, R 3a =CHCHCH3, R 3c =H
[0099] A 2.0 M solution of PhMgCI in THF (13 mL, 25.7 mmol) was added to a −78° C. solution of dimethylketene dithioacetal 10 (5.7 g, 19.8 mmol) in 200 mL of THF. After 3 h at −78° C., saturated aqueous NH 4 Cl was added and the layers were separated. The aqueous layer was extracted with EtOAc and the combined organic extracts were washed with water and brine, dried over Na 2 SO 4 , concentrated, and purified by column chromatography eluting with 20% EtOAc in hexanes to give 4.9 g (77%) of the thioenol ether as a yellow solid. MS m/z 321 (M+H).
[0100] Solid guanidine hydrochloride (1.5 g, 15.3 mmol) was added to a solution of the thioenol ether (4.9 g, 15.3 mmol) and K 2 CO 3 (2.6 g, 19.1 mmol) in 30 mL of DMF and the solution was heated to 80° C. After 6 h at 80° C., the solution was diluted with EtOAc and washed with water and brine. The organic layer was dried over Na 2 SO 4 , concentrated, and purified by column chromatography eluting with 40% EtOAc in hexanes to give 4.6 g (96%) of the pyrimidine regioisomers 11 as yellow solids. MS m/z 314 (M+H).
EXAMPLE 9
Synthesis of Aldehyde 13
R 2 =Ph
[0101] Solid MeSO 2 NH 2 (277 mg, 2.9 mmol) was added to a t-BuOH:H 2 O (1:1) solution (30 mL) of AD-mix-α (4.0 g). The resulting yellow solution was added to an EtOAc solution (15 mL) of the pyrimidine (910 mg, 2.9 mmol). After 3 days, solid sodium sulfite (4.4 g, 34.9 mmol) was added. After stirring for 1.5 h, the heterogeneous solution was diluted with EtOAc and the layers were separated. The aqueous phase was extracted with EtOAc and the combined extracts were washed with water and brine, dried over Na 2 SO 4 , concentrated, and purified by column chromatography eluting with 100% EtOAc to give 710 mg (70%) of the intermediate diol 12. MS m/z 348 (M+H).
[0102] Solid HlO 4 -2H 2 O (933 mg, 4.1 mmol) was added to a 0° C. solution of diol 12 (710 mg, 2.1 mmol) in THF. After 1.5 h at 0° C., the solution was diluted with EtOAc and the organic phase was washed with saturated aqueous NaHCO 3 , water, and brine. The organic layer was dried over Na 2 SO 4 and concentrated to give 603 mg (98%) of aldehyde 13 as a yellow solid that was used without further purification. MS m/z 302 (M+H).
EXAMPLE 10
Synthesis of Amine 14 via Reductive Amination
R 3a =N(—CH 2 CH 2 OCH 2 CH 2 —
[0103] Solid NaBH(OAc) 3 (53 mg, 0.25 mmol) was added to a solution of aldehyde 13 (50 mg, 0.17 mmol), morpholine (0.034 mL, 0.34 mmol), and AcOH (0.014 mL, 0.25 mmol) in 1 mL of THF. After 3 d the solution was filtered and concentrated. The resulting material was dissolved in CH 2 Cl 2 and washed with saturated aqueous NaHCO 3 and brine, dried over Na 2 SO 4 , concentrated, and purified by column chromatography eluting with 0-10% MeOH in CH 2 Cl 2 to give 38 mg (60%) of the amine 14 as a yellow solid. MS m/z 373 (M+H). The product was dissolved in a minimum amount of CH 2 Cl 2 and treated with 1.0 M HCl in ether to obtain the hydrochloride salt.
EXAMPLE 11
Cyclization to Form Dihydropyridine 16
R 2 =2-furyl, R 3 =H
[0104] To a solution of 3-dicyanovinylindan-1-one (4.06 g, 20.9 mmol) in 200 mL of ethanol was added 2-furaldehyde (3.01 g, 31.4 mmol) and 25 mL of conc. NH 4 OH. The solution was heated to reflux for 2 h and allowed to cool to rt overnight. The mixture was concentrated in vacuo to remove ethanol. The residue was filtered and washed with water. The purple solid obtained was dried to yield 5.92 g (89%). MS m/z 290 (M + +1).
EXAMPLE 12
Oxidation of Dihydropyridine 16 to Pyridine 17
R 2 =2-furyl, R 3 =H, R 4 =NH 2 , R 5 =CN, X=O
[0105] To a refluxing solution of dihydropyridine 16 (5.92 g, 20.4 mmol) in acetic acid (100 mL) was added a solution of chromium (VI) oxide (2.05 g, 20.4 mmol) in 12 mL of water. After 10 minutes at reflux, the reaction was diluted with water until a precipitate started to form. The mixture was cooled to room temperature and filtered. The residue was washed with water to give 4.64 g (79%) of a brown solid. MS m/z 288 (M + +1).
EXAMPLE 13
Reduction of Ketone 17 to Alcohol 18
R 2 =2-furyl, R 3 =H, R 4 =NH 2 , R 5 =CN, X=H. OH
[0106] To a 0° C. solution of ketone 17 (0.115 g, 0.40 mmol) in 12 mL of THF was added a 1.0 M LiAlH 4 solution in THF (0.40 mL, 0.40 mmol). The reaction was stirred at 0° C. for 1 h. The reaction was quenched by the addition of ethyl acetate (1.5 mL), water (1.5 mL), 10% aq. NaOH (1.5 mL), and saturated aq. NH 4 Cl (3.0 mL). The mixture was extracted with ethyl acetate (3×35 mL), washed with brine, and dried over sodium sulfate. The remaining solution was concentrated to yield 0.083 g (72%) of a yellow solid. MS m/z 290 (M + +1).
EXAMPLE 14
Hydrolysis of Nitrile 17 to Carboxylic Acid 19
R 2 =2-furyl, R 3 =H, R 4 =NH 2 , R 5 =COOH, X=O
[0107] To a mixture of nitrile 17 (0.695 g, 2.42 mmol) and ethanol (30 mL) was added 5 mL of 35% aqueous sodium hydroxide. The resulting mixture was heated to reflux overnight. After cooling to rt, the solution was poured into water and acidified with 1 N HCl. The resulting precipitate was isolated by filtration and washed with water to yield 0.623 g (84%) of a brown solid. MS m/z 329 (M + +23).
EXAMPLE 15
Synthesis of Carboxylic Ester 20 with Silver Carbonate
R 2 =2-furyl, R 3 =H, R 4 =NH 2 , R 5 =CO 2 CH 2 CH 2 NMe 2 , X=O
[0108] A suspension of carboxylic acid 19 (5.0 g, 16.3 mmol), silver carbonate (5.8 g, 21.2 mmol), and tetrabutylammonium iodide (1.5 g, 4.1 mmol) in 80 mL of DMF was heated to 90° C. After 1 h, the mixture was cooled to rt and 2-(dimethylamino)ethylchloride hydrochloride (2.4 g, 16.3 mmol) was added and the mixture was heated to 100° C. After 7 h, the reaction was filtered while hot, concentrated and purified by column chromatography eluting with 0-10% MeOH/CH 2 Cl 2 to yield 0.160 g (3%) of a yellow solid. MS m/z 378 (M + +1). The product was dissolved in a minimum of dichloromethane and treated with 1.0 M HCl in ether to obtain the hydrochloride salt.
EXAMPLE 16
Synthesis of Carboxylic Ester 20 with DEPC
R 2 =2-furyl, R 3 =H. R 4 =NH 2 , R 5 =CO 2 CH 2 CH(—CH 2 CH 2 CH 2 (Me)N—), X=O
[0109] To a mixture of carboxylic acid 19 (0.40 g, 1.3 mmol) and (S)-1-methyl-2-pyrrolidinemethanol (0.50 mL, 3.9 mmol) in DMF (30 mL) was added 0.20 mL (1.3 mmol) of diethylphosphoryl cyanide and triethylamine (0.20 mL, 1.3 mmol). The reaction was stirred at 0° C. for one hour and then heated up to approximately 70° C. overnight. The reaction was then cooled to rt and diluted with ethyl acetate. The organic mixture was washed with saturated aqueous NaHCO 3 , water, and brine. After being dried with sodium sulfate, the solution was concentrated. The residue was purified by column chromatography eluting with 10-100% ethyl acetate in hexane and then preparative TLC eluting with 2% MeOH in dichloromethane to yield 1.9 mg (0.4%) of a yellow solid. MS m/z 404 (M + +1).
EXAMPLE 17
Synthesis of Carboxylic Amide 21 with DEPC
R 2 =2-furyl, R 3 =H, R 4 =NH 2 , R 5 =CO 2 CH 2 CH(—CH 2 CH 2 CH 2 (Me)N—), X=O
[0110] To a mixture of carboxylic acid 19 (0.25 g, 0.82 mmol) and N,N,N′-trimethylethylenediamine (0.14 mL, 1.08 mmol) in DMF (20 mL) was added 0.12 mL (0.82 mmol) of diethylphosphoryl cyanide and triethylamine (0.11 mL, 0.82 mmol). The reaction was stirred at 0° C. for one hour and then heated up to approximately 60° C. overnight. The reaction was then cooled to rt and diluted with ethyl acetate. The organic mixture was washed with saturated aqueous NaHCO 3 , water, and brine. After being dried with magnesium sulfate, the solution was concentrated. The residue was purified by column chromatography eluting with 0-10% methanol in dichloromethane and then preparative TLC eluting with 1% MeOH in dichloromethane to yield 3.3 mg (10%) of a yellow solid. MS m/z 391 (M + +1). The product was dissolved in a minimum of diethyl ether and treated with 1.0 M HCl in ether to obtain the hydrochloride salt.
EXAMPLE 18
Synthesis of Carboxylic Amide 21 with EDCl
R 2 =2-furyl, R 3 =H, R 4 =NH 2 , R 5 =CON(—CH 2 CH 2 NMeCH 2 CH 2 —), X=O
[0111] A mixture of carboxylic acid 19 (0.300 g, 0.979 mmol), N-methylpiperazine (0.295 g, 2.94 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (0.563 g, 2.94 mmol) 1-hydroxybenzotriazole hydrate (0.397 g, 2.94 mmol), triethylamine (0.298 g, 2.94 mmol) in DMF (8 mL) was stirred at rt overnight. The mixture was then diluted with water and extracted several times with ethyl acetate. The combined organics were washed twice with brine and then dried over sodium sulfate. The solution was concentrated and then purified by column chromatography to afford 0.092 g (2%) of solid. MS m/z 389 (M + +1). The product was treated with 1.0 M HCl in ether to obtain the hydrochloride salt.
EXAMPLE 19
Synthesis of Carboxylic Ester 20 via a Dibromoalkane
R 2 =Ph, R 3 =H, R 4 =NH 2 , R 5 =CO 2 CH 2 CH 2 CH 2 NMe 2 , X=O
[0112] To a solution of carboxylic acid 19 (0.100 g, 0.32 mmol) in DMF (1.5 mL) was added 60% NaH dispersion in mineral oil (0.013 g, 0.32 mmol). After 10 min at rt, 1,3-dibromopropane (0.035 mL, 0.35 mmol) was added and the solution was stirred at rt for 17 h. After concentration, the residue was purified via column chromatography eluting with 40% ethyl acetate in hexanes to yield 0.014 g (9%) of a yellow solid. MS m/z 437 (M + +1).
[0113] To a solution of the yellow solid (0.014 mg, 0.03 mmol) in a sealed tube was added a 40% aqueous solution of dimethylamine (0.5 mL, 3.0 mmol). The tube was heated to 75° C. for 2 h before concentrating. The residue was purified by column chromatography eluting with 0-10% methanol in dichloromethane to yield 0.009 g (70%) of a yellow solid. MS m/z 402 (M + +1). The product was dissolved in a minimal amount of CH 2 Cl 2 and treated with 1 N HCl in ether to obtain the hydrochloride salt.
[0114] Following the general synthetic procedures outlined above and in Examples 1-19, the compounds of Table 1 below were prepared.
TABLE 1 MS No. R 2 R 3a R 3b R 3c R 3d R 4 X (M + 1) 1 4-MeOPh H H H H NH 2 CH 2 290 2 4-MeOPh H H H H NH 2 CO 304 3 2-furyl H H H H NH 2 CO 264 4 2-furyl H H H H NH 2 CH 2 250 5 3-pyridyl H H H H NH 2 CO 297 (+Na) 6 4-pyridyl H H H H NH 2 CO 275 7 H H H H NH 2 CO 281 8 4-ClC 6 H 4 H H H H NH 2 CO 308 9 3-NO 2 C 6 H 4 H H H H NH 2 CO 319 10 Ph H H H H NH 2 CO 274 11 3-MeOC 6 H 4 H H H H NH 2 CO 304 12 2-MeOC 6 H 4 H H H H NH 2 CO 304 13 3-HOC 6 H 4 H H H H NH 2 CO 290 14 2-thiophenyl H H H H NH 2 CO 302 15 3-thiophenyl H H H H NH 2 CO 302 16 2-furyl H Br H H NH 2 CO 342 17 2-furyl OH H H H NH 2 CO 280 18 SCH 3 NH 2 H H H NH 2 CO 259 19 3-FC 6 H 4 H H H H NCHNMe 2 CO 347 20 2-furyl NH 2 H H H NH 2 CO 279 21 2-furyl H H H NH 2 NH 2 CO 279 22 2-furyl H CF 3 H H NH 2 CO 332 23 2-furyl H H CF 3 H NH 2 CO 332 24 Ph H H H H NHMe CO 288 25 2-furyl H Cl Cl H NH 2 CO 332 26 2-furyl Cl H H Cl NH 2 CO 332 27 Ph H H H H N(CH 2 ) 2 NEt 2 CO 373 28 3,4-F 2 C 6 H 3 H H H H NH 2 CO 310 29 3,5-F 2 C 6 H 3 H H H H NH 2 CO 310 30 H H H H NH 2 CO 305 31 3,4,5-F 3 C 2 H 2 H H H H NH 2 CO 340 (M + Na) 32 Ph H H H NH 2 CO 348 33 Ph H H H NH 2 CO 348 34 H H H H NH 2 CO 333 35 2-furyl H H Br H NH 2 CO 342/344 36 2-furyl H H H F NH 2 CO 282 37 2-furyl MeO H H H NH 2 CO 294 38 4-FC 6 H 4 H H H H NH 2 CO 292 39 3-FC 6 H 4 H H H H NH 2 CO 292 40 SO 2 Me H H H H NH 2 CO 298 41 Sme H H H H NH 2 CO 266 42 Ome H H H H NH 2 CO 477 (2M + Na) 43 NHPh H H H H NH 2 CO 289 44 3-furyl H H H H NH 2 CO 264 45 5-methyl-2-furyl H H H H NH 2 CO 278 46 2-furyl OCH 2 CH 2 NHCO 2 tBu H H H NH 2 CO 437 47 Ph H H H H Me CO 297 48 Ph H H H H OMe CO 291 49 Ph CH 2 NMeCH 2 CH 2 NMe 2 H H H NH 2 CO 388 50 Ph H H H NH 2 CO 386 51 Ph H H H NH 2 CO 373 52 Ph CH 2 NEt 2 H H H NH 2 CO 359 53 Ph H H H NH 2 CO 371 54 Ph H H H NH 2 CO 429 55 Ph H H H NH 2 CO 443 56 Ph CH 2 NMeCH 2 CO 2 Me H H H NH 2 CO 389 57 Ph H H H NH 2 CO 401 58 Ph H H H NH 2 CO 416 59 Ph H H H NH 2 CO 414 60 Ph H H H NH 2 CO 486 61 Ph H H H NH 2 CO 422 62 Ph H H H NH 2 CO 397
[0115] TABLE 2 MS No. X R 2 R 3a R 3b R 3c R 3d R 1 (M + 1) 63 CO 2-furyl H H H H CN 288 64 CO Ph H H H H CN 298 65 CO Ph H H H H COOH 315 (M − 1) 66 CO 3-furyl H H H H CN 288 67 CO 3-FC 6 H 4 H H H H CN 316 68 CO 3-pyridyl H H H H CN 299 69 CO 2-furyl H H H H COOH 305 (M − 1) 70 CO 2-furyl H H H H CO 2 CH 2 CH 2 NMe 2 378 71 CO 4-FC 6 H 4 H H H H CN 316 72 CO 2-thiophenyl H H H H CN 304 73 CO 3-thiophenyl H H H H CN 304 74 CO 3-MeOC 6 H 4 H H H H CN 328 75 CO 2-imidazolyl H H H H CN 288 76 CO 2-furyl H H H H CONHCH 2 CH 2 NMe 2 377 77 CO 2-furyl H H H H CONMeCH 2 OH 2 NMe 2 391 78 CO 2-furyl H H H H CONHCHMeCH 2 NMe 2 391 79 CO 2-furyl F F F F CN 358 (M − 1) 80 CO 2-furyl H H H H 389 81 CO Ph H H H H CO 2 CH 2 CH 2 NMe 2 388 82 CO 2-furyl H H H H 404 83 CO Ph H H H H 457 84 CO Ph H H H H 444 85 CO Et H H H H CN 250 86 CO i-Bu H H H H CN 278 87 CO Ph H H H H CO 2 CH 2 CH 2 CH 2 NMe 2 402 88 CO Ph H H H H 414 89 CHOH 2-furyl H H H H CN 290 90 CO Ph H H H H 414 91 CO Ph H H H H 430 92 CO Ph H H H H CO 2 CH 2 CHMeCH 2 NMe 2 416 93 CO 3-thiophenyl H H H H CO 2 CH 2 CH 2 NMe 2 394 94 CO CH 2 CH 2 CHCH 2 H H H H CN 276 95 CO c-Hex H H H H CN 302 (M − 1) 96 CO 2-furyl H H H H (S)—CO 2 CHMeCH 2 NMe 2 392
III. Biological Assays and Activity
Ligand Binding Assay for Adenosine A2a Receptor
[0116] Ligand binding assay of adenosine A2a receptor was performed using plasma membrane of HEK293 cells containing human A2a adenosine receptor (PerkinElmer, RB-HA2a) and radioligand [ 3 H]CGS21680 (PerkinElmer, NET1021). Assay was set up in 96-well polypropylene plate in total volume of 200 μL by sequentially adding 20 μL1:20 diluted membrane, 130 μL assay buffer (50 mM Tris.HCl, pH7.4 10 mM MgCl 2 , 1 mM EDTA) containing [ 3 H] CGS21680, 50 μL diluted compound (4×) or vehicle control in assay buffer. Nonspecific binding was determined by 80 mM NECA. Reaction was carried out at room temperature for 2 hours before filtering through 96-well GF/C filter plate pre-soaked in 50 mM Tris.HCl, pH7.4 containing 0.3% polyethylenimine. Plates were then washed 5 times with cold 50 mM Tris.HCl, pH7.4, dried and sealed at the bottom. Microscintillation fluid 30 μl was added to each well and the top sealed. Plates were counted on Packard Topcount for [ 3 H]. Data was analyzed in Microsoft Excel and GraphPad Prism programs. (Varani, K.; Gessi, S.; Dalpiaz, A.; Borea, P. A. British Journal of Pharmacology, 1996, 117, 1693)
[0000] Adenosine A2a Receptor Functional Assay
[0117] CHO-K1 cells overexpressing human adenosine A2a receptors and containing cAMP-inducible beta-galactosidase reporter gene were seeded at 40-50 K/well into 96-well tissue culture plates and cultured for two days. On assay day, cells were washed once with 200 μL assay medium (F-12 nutrient mixture/0.1% BSA). For agonist assay, adenosine A2a receptor agonist NECA was subsequently added and cell incubated at 37° C., 5% CO 2 for 5 hrs before stopping reaction. In the case of antagonist assay, cells were incubated with antagonists for 5 minutes at R.T. followed by addition of 50 nM NECA. Cells were then incubated at 37° C., 5% CO 2 for 5 hrs before stopping experiments by washing cells with PBS twice. 50 μL 1× lysis buffer (Promega, 5× stock solution, needs to be diluted to 1× before use) was added to each well and plates frozen at −20° C. For β-galactosidase enzyme calorimetric assay, plates were thawed out at room temperature and 50 μL 2× assay buffer (Promega) added to each well. Color was allowed to develop at 37° C. for 1 h or until reasonable signal appeared. Reaction was then stopped with 150 μL 1 M sodium carbonate. Plates were counted at 405 nm on Vmax Machine (Molecular Devices). Data was analyzed in Microsoft Excel and GraphPad Prism programs. (Chen, W. B.; Shields, T. S.; Cone, R. D. Analytical Biochemistry, 1995, 226, 349; Stiles, G. Journal of Biological Chemistry, 1992, 267, 6451)
[0000] Haloperidol-Induced Catalepsy Study in C57bl/6 Mice
[0118] Mature male C57bl/6 mice (9-12 week old from ACE) were housed two per cage in a rodent room. Room temperature was maintained at 64-79 degrees and humidity at 30-70% and room lighting at 12 hrs light/12 hrs dark cycle. On the study day, mice were transferred to the study room. The mice were injected subcutaneously with haloperidol (Sigma H1512, 1.0 mg/ml made in 0.3% tartaric acid, then diluted to 0.2 mg/ml with saline) or vehicle at 1.5 mg/kg, 7.5 ml/kg. The mice were then placed in their home cages with access to water and food. 30 minutes later, the mice were orally dosed with vehicle (0.3% Tween 80 in saline) or compounds at 10 mg/kg, 10 ml/kg (compounds, 1 mg/ml, made in 0.3% Tween 80 in saline, sonicated to obtain a uniform suspension). The mice were then placed in their home cages with access to water and food. 1 hour after oral dose, the catalepsy test was performed. A vertical metal-wire grid (1.0 cm squares) was used for the test. The mice were placed on the grid and given a few seconds to settle down and their immobility time was recorded until the mice moved their back paw(s). The mice were removed gently from the grid and put back on the grid and their immobility time was counted again. The measurement was repeated three times. The average of three measurements was used for data analysis.
[0119] Compound 70 showed 87% inhibition and compound 3 showed 90% inhibition of haloperidol-induced catalepsy when orally dosed at 10 mg/kg.
TABLE 5 Ki (nM) A2a A1 A2a antagonist antagonist No. binding function function 1 44.64 233.7 52.98 2 2.032 6.868 5.32 3 0.26 0.0066 0.288 4 0.885 2.63 15.57 5 5.355 9.64 27.1 6 3.9 4.56 16.44 7 0.26 0.49 6.89 8 58.41 5.5 11.59 9 20.82 4.85 7.69 10 6.1 0.109 1.2 11 8.85 1.63 2.47 12 33.49 32.52 172.3 13 5.16 35.59 10.35 14 2.19 0.59 3.19 15 3.23 0.258 3.46 16 1.75 0.169 5.22 17 6.3 67.14 111.29 18 317.95 >3000 188.99 19 110.73 20.88 21.64 20 0.05 0.126 0.91 21 0.376 0.053 3.51 22 14.16 0.055 2.75 23 13.58 0.55 1.47 24 30.32 >3000 5.99 25 172.85 5.69 17.44 26 34.57 0.88 3.13 27 146.84 68.28 >1000 28 48.9 3.53 5.86 29 20.95 1.42 4.27 30 31.55 10.15 4.05 31 140.68 15.22 17.5 32 3.55 0.634 9.89 33 0.175 0.34 0.021 34 560.13 35 3.49 0.265 7.09 36 4.37 0.052 2.52 37 2.86 0.143 3.07 38 2.34 0.956 9.44 39 4.92 0.926 2.31 40 2720.46 41 88.01 575.43 >3000 42 118.2 782.18 >10000 43 39.9 3.68 2.34 44 3.93 0.208 7.4 45 4.013 0.005 0.016 46 60.56 490.14 32.54 47 1076.76 48 470.84 >1000 >1000 49 51.12 40.13 119.03 50 80.15 11.31 94.24 51 36.81 3.26 32.92 52 94.41 18.33 107.17 53 64.15 14.25 40.82 54 40.79 3.19 19.56 55 32.82 5.84 19.86 56 25.72 6.81 25.76 57 34.02 15.93 39.29 58 30.65 11.65 60.99 59 40.79 7.94 34.11 60 34.29 61 29.83 62 58.39 63 0.59 0.0002 0.18 64 13.09 0.138 4.61 65 574.71 244.96 163.36 66 4.21 0.069 15.59 67 13.4 0.618 4.37 68 7.59 0.73 34.84 69 2261 90.16 >1000 70 9.89 0.44 20.13 71 17.24 3.39 2.42 72 12.64 2.54 6.24 73 4.925 0.06 9.7 74 14.67 5.7 7.28 75 23.72 1.51 78.33 76 33.03 22.13 >500 77 6.254 0.68 >500 78 17.65 1.58 >500 79 8.03 12.48 >1000 80 69.08 15.86 55.99 81 228.7 29.03 33.63 82 20.24 1.36 29.58 83 200.06 74.87 117.05 84 173.98 24.71 27.42 85 507.72 86 244.07 >1000 39.26 87 98.93 39.45 >300 88 129.6 48.87 >300 89 5.85 1.12 11.16 90 202.17 57.7 >300 91 208.32 22.07 14.67 92 38.82 13.9 32.88 93 64.05 23.57 104.31 94 49.55 >1000 35.99 95 338.13 >1000 110.22 96 48.55 10.08 52.45
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This invention provides novel arylindenopyridines and arylindenopyrimidines of the formula:
wherein R 1 , R 2 , R 3 , R 4 , and X are as defined above, and pharmaceutical compositions comprising same, useful for treating disorders ameliorated by antagonizing adenosine A2a receptors. This invention also provides therapeutic and prophylactic methods using the instant compounds and pharmaceutical compositions.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates generally to a powertrain for a hybrid electric vehicle (HEV), and, in particular to a method for performing transmission input torque modulation during a change to a higher gear.
[0003] 2. Description of the Prior Art
[0004] In a conventional vehicle equipped with a transmission that produces step changes among gear ratios, the driver can experience driveline disturbances during a gear shift. The driveline disturbances occur due to the acceleration and deceleration of the engine and transmission component inertias, which produce an inertial torque during the gear shift. In the case of an upshift, the transmission output torque increases during the ratio change phase of the gear shift as a result of the engine speed changing.
[0005] This output torque disturbance is directly felt by occupants of the vehicle and affects shift quality. The level of output shaft torque disturbance increases with the speed of the upshift since engine deceleration is greater with faster gear shifts. By reducing engine torque produced during the upshift, inertial torque can be offset and the output shaft torque increase can be minimized, thereby improving shift quality. The method of reducing engine torque produced during the upshift is referred to as “input torque modulation” control.
[0006] In the case of a downshift, the transmission output torque decreases during the ratio change phase as the engine and transmission components accelerate to the synchronous speed for the lower gear. Moreover, during the torque transfer phase of the downshift, the transmission output torque can spike near the completion of the downshift as the engine accelerates. The drop in output torque during the ratio change is directly felt by the vehicle occupants and can give the sense of an acceleration discontinuity as the downshift is performed. The output torque spike at the end of the downshift can affect shift quality and produce a feeling of a rough shift. Furthermore, the level of output shaft torque drop and spike near the end of the downshift will increase in proportion to speed of the downshift.
[0007] By using input torque modulation, the engine combustion torque can be reduced near the end of the downshift in order to reduce the engine's acceleration as the shift ends. As a result, the transmission output torque spike can be minimized and avoided, thereby reducing the shift disturbance.
[0008] In conventional vehicle applications, limitations and problems with input torque modulation during gear shifts include limited engine torque reduction authority due to constraints, such as emissions; delayed engine torque response to torque modulation requests, further degrading shift quality; and poor fuel efficiency, since spark retardation is commonly used for achieving torque modulation requests.
SUMMARY OF THE INVENTION
[0009] In a powertrain for motor vehicle that includes an engine, an electric machine able to function alternately as a motor and a generator, and a transmission whose input is driveably connected to the engine and the electric machine, a method for controlling transmission input torque during an upshift including using the engine to produce torque transmitted to the transmission input, during the ratio change phase of the upshift, operating the electric machine as a generator, and during an ratio change phase of the upshift, controlling a net torque transmitted to the transmission input by using the engine to drive the transmission and the electric machine concurrently. The engine torque and torque required to drive the electric machine can be varied during the ratio change phase.
[0010] During a transmission shift event, the electric machine is controlled to produce accurately a transmission input torque modulation request. By taking advantage of the electric machine's capability, output shaft torque disturbances are reduced and optimum shift quality is achieved.
[0011] The transmission input torque modulation control strategy can be applied to HEV powertrains including rear wheel drive, front wheel drive and all wheel drive configurations, full HEV, mild HEV having at least one electric machine at the transmission input. Furthermore, this control strategy is applicable to conventional automatic transmission, dual clutch powershift transmissions, and converterless automatic transmissions.
[0012] The scope of applicability of the preferred embodiment will become apparent from the following detailed description, claims and drawings. It should be understood, that the description and specific examples, although indicating preferred embodiments of the invention, are given by way of illustration only. Various changes and modifications to the described embodiments and examples will become apparent to those skilled in the art.
DESCRIPTION OF THE DRAWINGS
[0013] The invention will be more readily understood by reference to the following description, taken with the accompanying drawings, in which:
[0014] FIG. 1 is a schematic diagram showing an automotive vehicle powertrain for a hybrid electric vehicle;
[0015] FIG. 2 is a schematic diagram showing propulsion and power flow of the vehicle powertrain of FIG. 1 ;
[0016] FIG. 3 is a schematic diagram showing vectors representing torque transmission among components of the powertrain operating in mode A;
[0017] FIG. 4 is a schematic diagram showing vectors representing torque transmission among components of the powertrain operating in mode B;
[0018] FIGS. 5A-5D illustrate the change of powertrain variables during a transmission upshift performed with input torque modulation;
[0019] FIGS. 6A-6D illustrate the change of powertrain variables during a transmission downshift performed with input torque modulation;
[0020] FIG. 7 is a logic flow diagram of an algorithm for providing input torque modulation transmission control in the HEV powertrain of FIG. 1 ;
[0021] FIG. 8 is a logic flow diagram of an algorithm for selecting the operating mode of the powertrain of FIG. 1 during input torque modulation control; and
[0022] FIG. 9 is a schematic diagram showing vectors representing torque transmission among components of the powertrain operating in mode C.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0023] Referring first to FIGS. 1 and 2 , the powertrain 10 configuration includes a first power source such as an internal combustion engine 12 , a diesel engine or a gasoline engine; a power transmission 14 driveably for producing multiple forward and reverse gear ratios, such as a wet-clutch powershift transmission; an electric machine 16 driveably connected to the engine crankshaft and transmission input 18 , such as a crankshaft-integrated starter/generator (CISG) for providing starter/generator capability; and an additional electric machine 20 driveably connected to a rear axle differential mechanism 36 , such as an electric rear axle drive (ERAD), for providing additional propulsion capability in either an electric drive or hybrid drive mode. The transmission output 24 is connected through a final drive unit and differential mechanism 26 to the front axles 28 , 30 , which drive the front wheels 32 , 33 , respectively. ERAD 20 drives the rear wheels 34 , 35 through ERAD gearing 48 , a differential mechanism 36 , rear axles 22 , 23 and wheels 34 , 35 .
[0024] The powertrain 10 comprises a first power path driveably connected to the load that includes CISG 16 , transmission 14 , final drive unit 26 , axles 28 , 30 and the wheels 32 , 33 . A gear of the transmission must be engaged between input 18 and output 24 and the input clutch 38 or 39 that is associated with the engaged gear must be engaged to complete a drive path between CISG 16 and the vehicle wheels 32 , 33 . Powertrain 10 also comprises a second power path driveably connected to the load that includes ERAD 20 , ERAD gearing 48 , a differential mechanism 36 , rear axles 22 , 23 and wheels 34 , 35 .
[0025] An electronic engine control module (ECM) 24 controls operation of engine 12 . An electronic transmission control module (TCM) 27 controls operation of transmission 14 and the input clutches 38 , 39 . An integrated starter controller (ISC) 40 controls operation of CISG 16 , ERAD 20 and the system for charging an electric storage battery 42 , which is electrically coupled to the electric machines 16 , 20 .
[0026] FIG. 2 shows the power and energy flow paths from the power sources 12 , 16 , 20 to the load at the vehicle wheels 32 - 35 . Power produced by engine 12 and power produced by CISG 16 are combined at 44 and transmitted to the transmission input 18 . Electric power produced by both electric machines 16 , 20 is combinable at 46 for charging the battery 42 , or is transmitted from the battery to the electric machines. Mechanical power produced by ERAD 20 is transmitted through ERAD gearing 48 to the load at the rear wheels 34 , 35 through the rear final drive 36 .
[0027] In a hybrid electric vehicle application in which a fixed-ratio transmission is used and at least one electric machine is coupled to the engine crankshaft 18 to provide engine start/stop capability such as a crankshaft integrated starter/generator (CISG) 16 , enhanced input torque modulation can be provided during transmission shifts in a superior method compared to that of a conventional input torque modulation strategy.
[0028] As shown in FIGS. 3 and 4 , operating modes of the powertrain 10 are used to provide transmission input torque modulation during transmission shift events. Depending on the type of shift event, i.e., an upshift or downshift, level of torque modulation request, CISG operating conditions, battery conditions, and other factors, the appropriate powertrain operating mode will be used to provide the desired input torque modulation request. FIG. 3 is a schematic diagram of the powertrain 10 showing vectors representing torque transmission among components during operating mode A, in which the CISG 16 reduces transmission output torque during an upshift.
[0029] FIGS. 5A-5D illustrate the change of certain powertrain variables during a transmission upshift in which input torque modulation is provided by the CISG 16 using operating mode A, whose power flow among powertrain components is illustrated in FIG. 3 . In operating mode A, CISG 16 operates as an electric generator to provide input torque modulation and to reduce the transmission output torque disturbance 50 that would result if no torque modulation were being performed. CISG is operative for this purpose provided that the CISG is available, i.e., its current temperature is less than its temperature limit, its speed is less than its operational speed limit, etc., and the battery state of charge (SOC) is below the maximum allowable limit.
[0030] In operating mode A, CISG 16 is driven by engine 12 , thereby reducing the net torque 52 transmitted by crankshaft 18 to the input of transmission 14 during the ratio change phase 54 of the upshift, i.e., while the change gear ratio change 56 is occurring following the torque transfer phase 55 . The negative CISG torque 58 which is controlled to provide input torque modulation during the shift is shown in FIG. 5D . As shown in FIG. 5C , excess torque 60 produced by engine 12 during the ratio change phase is recovered and converted into electrical energy that is stored by the battery 42 , while achieving the requested input torque modulation and providing optimum shift quality. FIG. 5A illustrates the difference 62 between the magnitude of torque 64 at the transmission output shaft 24 with CISG 16 providing input torque modulation for optimum shift quality and the output torque 50 with no input torque modulation provided.
[0031] Delays in crankshaft torque reduction can be avoided by taking advantage of the responsiveness of CISG 16 thus leading to accurate input torque modulation levels. Operating mode A can also be used with both CISG 16 and engine 12 reducing the net crankshaft torque to meet the requested input torque modulation level. This is useful in the case where the CISG may not be fully available for input torque modulation or the battery SOC is near its maximum limit.
[0032] FIGS. 6A-6D illustrate the change of certain powertrain variables during a transmission downshift in which input torque modulation is provided by the CISG 16 using both operating modes A and B , whose power flow among powertrain components is illustrated in FIGS. 3 and 4 , respectively.
[0033] As FIG. 6A shows, during the ratio change or ratio change phase 54 of the downshift, powertrain 10 is placed in operating mode B as shown in FIG. 4 , wherein CISG 16 operates as an electric motor to increase the transmission output torque to a level 68 rather than a output torque drop 76 that would result if no torque modulation were being performed. During the ratio change phase 54 of the downshift, CISG torque 70 supplements the engine torque 72 so that the net crankshaft torque 74 is increased to output shaft torque level 68 in order to offset the transmission output torque decrease 76 , which would occur without torque modulation. This would provide acceleration continuity during the downshift and improved shift performance.
[0034] Operating mode B is used provided that the CISG 16 is available, i.e., its current temperature is less than its temperature limit, its speed is less than its operational speed limit, and the battery state of charge (SOC) is greater than the minimum allowable limit. This CISG capability is unique to that of an HEV since the CISG can be used to offset the output torque drop 76 so that the driver can sense acceleration continuity during the downshift.
[0035] During the torque transfer phase 55 near the completion of the downshift, as shown in FIGS. 6A and 6C , powertrain 10 functions in operating mode A with CISG 16 operating as a electric generator in order to provide input torque modulation. As shown in FIGS. 6C and 6D , CISG 16 is controlled to a negative torque 78 near the end of the downshift during the torque transfer phase to provide torque modulation so that the net crankshaft torque 74 is reduced in order to minimize or eliminate the transmission output torque spike 80 , which would normally occur without the CISG providing torque modulation. This excess crankshaft torque 82 produced by the engine 12 is converted to electrical energy and stored by the battery 42 , while achieving the requested input torque modulation and providing optimum shift quality. Moreover, by taking advantage of the responsiveness of CISG 16 , delays in crankshaft torque reduction can be avoided thus leading to accurate input torque modulation control during the downshift.
[0036] FIG. 7 shows the steps of an algorithm for providing input torque modulation transmission control of the HEV powertrain of FIG. 1 . After execution of the algorithm is started and the operating conditions of powertrain 10 are assessed at step 90 , a test is performed at step 92 to determine whether a gear ratio change of the transmission 14 has been requested by a transmission controller acting in response to vehicle parameters that include without limitation engine throttle position, accelerator pedal position, vehicle speed, engine speed, the position of a manually operated gear selector, and a schedule of the preferred gear ratios related to the vehicle parameters.
[0037] If the result of test 92 is logically positive, control advances to step 94 where a test is performed to determine whether shift input torque modulation is requested by the controller. If the result of either test 92 or 94 is logically negative, control returns to step 90 . But if the result of test 94 is positive, the magnitude of desired input torque modulation is determined at step 96 . The desired magnitude of input torque modulation is determined based on the shift event progress. For example, at the beginning of the ratio change phase of an upshift, the desired magnitude will ramp from zero to a negative steady-state level as the ratio change continues and will ramp back to zero as the ratio change phase is completed.
[0038] At step 98 , the operating mode of powertrain 10 is selected in accordance with the algorithm of FIG. 8 upon reference to current operating parameters and the desired magnitude of input torque modulation.
[0039] At step 100 , powertrain 10 is placed in the desired operating mode selected by algorithm of FIG. 8 in order to provide the desired input torque modulation during the shift event.
[0040] Referring now to the algorithm for selecting the desired operating mode shown in FIG. 8 , a test is performed at step 102 to determine whether the CISG temperature is less than a high temperature reference.
[0041] If the result of test 102 is positive, a test is performed at step 104 to determine whether the speed of CISG 16 is less than a reference speed representing the maximum allowable operating speed of the CISG.
[0042] If the result of test 104 is positive, a test is performed at step 106 to determine whether the magnitude of a request for transmission input torque modulation is less than a reference torque limit representing the current maximum torque capability of CISG 16 .
[0043] If the result of any of tests 102 , 104 or 106 is negative, control advances to step 108 , where powertrain 10 is placed in operating mode C, in which torque produced by engine 12 alone is transmitted to transmission output 24 without CISG torque affecting any change in torque carried on crankshaft 18 to the transmission input and CISG 16 neither produces or draws power. Operating mode C, shown in FIG. 9 , is that of a conventional vehicle and the engine torque will be reduced to provide the desired level of input torque modulation since the CISG cannot be used.
[0044] If the result of test 106 is positive, a test is performed at step 110 to determine whether the desired magnitude of transmission input torque modulation is negative. If the result of test 110 is positive indicating that the desired input torque modulation level is negative and the crankshaft torque is to be reduced, a test is performed at step 112 to determine whether the battery SOC is less than a maximum allowable SOC reference.
[0045] If the result of test 112 is positive indicating that the battery SOC can be further increased as the CISG is operated as an electric generator, at step 114 operating mode A is selected, indicating that CISG 16 is available for input torque modulation by converting power produced by engine 12 into electrical energy to be stored by the battery during an upshift or downshift while achieving the desired input torque modulation level.
[0046] If the result of any of test 112 is negative indicating that the battery SOC cannot be further increased, control advances to step 108 , where powertrain 10 is placed in operating mode C, in which torque produced by engine 12 alone is transmitted to transmission output 24 without CISG torque affecting any change in torque carried on crankshaft 18 to the transmission input and CISG 16 neither produces or draws power.
[0047] If the result of test 110 is negative indicating that the desired input torque modulation level is positive and the crankshaft torque is to be increased, a test is performed at step 116 to determine whether the battery SOC is less than a minimum SOC before operating the CISG as an electric motor and discharging the battery.
[0048] If the result of test 116 is positive, at step 118 operating mode B is selected, indicating that CISG 16 is available for torque modulation by supplementing power produced by engine 12 during a downshift.
[0049] If the result of test 116 is negative, control advances to step 108 , where powertrain 10 is placed in operating mode C, in which torque produced by engine 12 alone is transmitted to transmission output 24 without CISG torque affecting any change in torque carried on crankshaft 18 .
[0050] In accordance with the provisions of the patent statutes, the preferred embodiment has been described. However, it should be noted that the alternate embodiments can be practiced otherwise than as specifically illustrated and described.
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In a powertrain for motor vehicle that includes an engine, an electric machine able to function alternately as a motor and a generator, and a transmission whose input is driveably connected to the engine and the electric machine, a method for controlling transmission input torque during an upshift including using the engine to produce torque transmitted to the transmission input, during the ratio change phase of the upshift, operating the electric machine as a generator, and during the ratio change phase of the upshift, controlling a net torque transmitted to the transmission input by using the engine to drive the transmission and the electric machine concurrently.
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BACKGROUND OF THE INVENTION
The present invention is directed to a control device for controlling bicycle operating components and, more specifically, to a control device for operating brakes, bicycle transmissions such as hubs and derailleurs, and other devices.
With a conventional bicycle control device, the control displacement of a lever or knob controlled by hand is transmitted to a winder that is linked to one end of a control cable, and this winder reels the control cable in or out depending on the direction of this control displacement. Movement of the control cable results in the actuation of a working device such as a derailleur or brake linked to the other end of the control cable. Cable mechanisms work very well when the position between the manual lever or knob and the winder is in a twisted relation, or in cases in which there is a large gap between the manual lever or knob and the winder.
A bicycle shifting control device in which such a cable mechanism is used is known from Japanese Laid-Open Patent Application 5-270475, for example. With this shifting control device, a manual knob and a winder are linked by a relay cable, and a shifting cable that is linked to the shifter is also linked to the winder. In order to lighten the operating effort required by the manual knob, the winding diameter of the relay cable is made greater than the winding diameter of the shifting cable. With such a device, however, reducing the operating effort by half requires that the winding diameter of the relay cable be twice the winding diameter of the shifting cable, so the winder becomes bulky. As a result the overall shifting control device is large. Consequently, there are problems with a shifting control device such as that described above in terms of mounting site options and the degree of design freedom.
SUMMARY OF THE INVENTION
The present invention is directed to a bicycle control device which provides light operating effort but with a compact and simple construction. In one embodiment of the present invention, a base member is provided for attachment to a structural member of the bicycle, and a control member is mounted for movement relative to the base member. Another member has a first end secured relative to the base member and a second end secured relative to the control member so that movement of the control member relative to the base member causes the first end of the member to move relative to the second end of the member. A linking member is disposed between the first end of the member and the second end of the member for movement with the member. The linking member has an attachment location for attaching a control element of the bicycle to the linking member. The device may then operate according to the principle of a running block.
In a more specific embodiment, the member comprises a cable, and the linking member is disposed for sliding along the cable when the control member moves relative to the base member. The linking member may include a curved surface about which the cable winds, wherein an angle formed by the cable as it deflects about the linking member is between approximately 120 degrees and approximately 180 degrees. In another embodiment, the linking member may include a pulley about which the cable winds. The base member may include a curved peripheral surface and a guide disposed thereon, wherein the linking member is disposed for sliding along the guide. The guide may be oriented generally perpendicular to an axis, and this axis may be oriented generally parallel to the axis of rotation of the control member. Alternatively, the axis may be slanted relative to the axis of rotation.
In another embodiment which provides for multiple levels of force multiplication, a base member is provided for attachment to a structural member of the bicycle, and a control member is mounted for movement relative to the base member. A first member (40a) has a first end secured relative to the base member and a second end secured relative to the control member so that movement of the control member relative to the base member causes the first end of the first member to move relative to the second end of the first member, and a first linking member is disposed between the first end of the first member and the second end of the first member for movement with the first member. A second member has a first end secured relative to the base member and a second end secured relative to the first linking member so that movement of the first linking member relative to the base member causes the first end of the second member to move relative to the second end of the second member. A second linking member is disposed between the first end of the second member and the second end of the second member for movement with the second member, and the second linking member has an attachment location for attaching a control element of the bicycle to the second linking member.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an external view of a particular embodiment of a bicycle control device according to the present invention;
FIGS. 2a-2b diagrams illustrating theories of operation of various embodiments of the present invention;
FIG. 3 is a partially cut away oblique view of a particular embodiment of the shifting control device shown in FIG. 1;
FIG. 4 is a front internal view of a particular embodiment of the shifting control device shown in FIG. 1;
FIG. 5 is a side cross-sectional view of a particular embodiment of the shifting control device shown in FIG. 1;
FIG. 6 is a front view of a particular embodiment of a base member used in the shifting control device shown in FIG. 1;
FIG. 7 is a side view of a particular embodiment of a sliding piece according to the present invention used to pull an actuating cable;
FIG. 8 is a detailed view of a particular embodiment of a curved opening in the sliding piece shown in FIG. 7;
FIG. 9 is a front view of an alternative embodiment of a base member used in the shifting control device shown in FIG. 1; and
FIG. 10 is a side view of an alternative embodiment of a sliding piece according to the present invention used to pull an actuating cable.
DETAILED DESCRIPTION OF THE EMBODIMENTS
FIG. 1 shows a shifting control device 1 that has been mounted on the handlebar of a bicycle (not shown here) in order to control a derailleur or other such shifting device (as a working device of the bicycle) via a control cable 2. This shifting control device 1 is inserted in and attached to a handlebar 3 next to a grip 4 formed at the end of the handlebar 3, and is equipped with a rotary control 20 that is rotated around the handlebar 3 by the thumb, index finger, etc., of the hand that grips the handlebar
FIG. 2a shows the principle construction of this shifting control device 1. The specifics thereof are shown in FIG. 4 as a side view of FIG. 3, which is a partially cut-away oblique view. The shifting control device 1 is equipped with a base member 10 formed in a ring shape that is fitted over and fixed to the handlebar 3, and a rotary control ring 20 that is rotatably mounted as the control member around the outside surface of this base member 10. A relay cable 40 is linked at one end to the base member 10 by a first linking means 50 and at the other end to the rotary control ring 20 by a second linking means 60. A deflection means 30 is guided through a guide groove 11 formed in a spiral around the outside surface of the above-mentioned base member 10. The deflection means 30 deflects the extension direction of the relay cable 40 in the opposite direction by being wound with the middle region of the relay cable 40.
The first linking means 50 comprises [i] a stepped through hole 12 provided to the flange of the above-mentioned base member 10 in parallel to the axis X and [ii] an anti-slip nipple that is connected to the end of the relay cable 40 that has passed through the small diameter portion 12a of this stepped through hole 12 and that is housed in the large diameter portion 12b of this stepped through hole 12. The second linking means 60 has essentially the same structure as the above-mentioned first linking means 50, so detailed illustration and description thereof will be omitted here.
To facilitate understanding, the base member 10 is shown in FIG. 6 in a state prior to its attachment. The basic shape is one of a cylinder with relatively thin walls provided with a through hole having an axis X through which the handlebar 3 will be inserted. A control cable guide nozzle 13, provided with a small diameter hole through which the inner cable 2a of the control cable 2 is passed and a large diameter hole in which the outer cable 2b is fixed, projects outward in the diameter direction from one side of this base member 10. A guide groove 11 that extends in a direction that is slightly slanted from the diameter direction is formed around the outside surface of the cylinder corresponding to this nozzle 13. In other words, this guide groove 11 is in the form of a spiral.
Numerous elastically deformable engagement teeth 14 are formed in a row in the circumferential direction around the outside surface of the other side of this cylinder in order to rotatably support the above-mentioned rotary control ring 20 while adding frictional force. In hand with this, numerous engagement detents 21 that engage with the above-mentioned engagement teeth 14 are formed around the inside surface of the above-mentioned rotary control ring 20, as can be seen in FIG. 5. The shape and dimensions of these engagement teeth 14 and engagement detents 21 are determined such that the rotary control ring 20 can rotate smoothly with a clicking feel around the outside surface of this base member, and such that the ring can be supported at any engagement position. Further, protrusions 22 are formed around the outside surface of the rotary control ring 20 so that good tactile feel will be achieved.
In this embodiment, as shown in FIG. 7, the deflection means 30 is formed as a sliding piece that slides along a guide groove 11 formed in the base member 10, and the shape thereof is essentially that of a partial spiral. A cable fixing hole 32 that is used to fix the end of the inner cable 2a of the control cable 2, and a curved opening 31 through which the relay cable 40 is inserted are provided. A floor 33 that functions as the sliding surface for this sliding piece 30 is worked such that it matches up with a guide surface 11a, which is the bottom of the guide groove 11, which allows for smooth sliding of the sliding piece 30. As is clear from FIG. 8, the curved opening 31 is formed such that the relay cable 40 enters from one sliding direction of the sliding piece 30 and exits in the other direction. A construction in which the heading of the relay cable 40 is deflected by such a curved surface can be produced by molding and working or by sintering, and therefore contributes to a cost reduction during mass production of the deflection means 30.
When tension acts on the relay cable 40, a force that attempts to slide the sliding piece 30 acts on the curved surface 31a on the inside of the curved opening 31. Since, as mentioned above, the inner cable 2a of the control cable 2 is fixed to this sliding piece 30, the work of the sliding piece 30 is transmitted to the shifter or other bicycle working device via the inner cable 2a. In other words, this sliding piece 30 functions as the running block in the principle diagram of FIG. 2a.
The operation of the shifting control device 1 discussed above will now be described.
In FIG. 3, when the rotary control ring 20 is rotated in the direction of the arrow R (hereinafter this direction will be referred to as counterclockwise), the tension on the relay cable 40 increases, and this slides the sliding piece 30 counterclockwise along the guide groove 11. As is clear from FIG. 4, the counterclockwise sliding of the sliding piece 30 pulls the inner cable 2a of the control cable 2, and the displacement of this inner cable 2a is transmitted to a derailleur (not shown here), where a shift to a different speed is made (such as shifting up). A derailleur is ordinarily equipped with a return spring, and as a result the spring acts to return the rotary control ring 20 in the clockwise direction so that the sliding piece 30 will slide clockwise. However, the rotary control ring 20 stays put in the desired control position as a result of the positional maintenance force created by the above-mentioned elastically deformable engagement teeth 14 and engagement detents 21. Further counterclockwise rotation of the rotary control ring 20 allows the derailleur speed level to be shifted successively by the same working process.
As is clear from FIG. 2a, which illustrates the principle of the shifting control device of the present invention, the operation effort during shifting is lighter because the rotary control ring 20 pulls the inner cable 2a at about twice the force as the pulling force applied to the relay cable 40 by the principle of a running block.
Next, when the rotary control ring 20 is rotated clockwise, there is a reduction in the tension on the relay cable 40, and as a result the sliding piece 30 slides clockwise along the guide groove 11 while being pulled by the inner cable 2a. Displacement of the inner cable 2a in the direction opposite to the previous direction results in a shifting of speeds by the derailleur in the opposite direction (such as shifting down).
For the sake of visual confirmation of the relation between the rotational control displacement position of the rotary control ting 20 and the speed level of the derailleur effected thereby, graduations can be provided around the outside surface of a cover 70 as shown partially and in simplified fashion in FIG. 3, and an indicator needle that corresponds to these graduations can be provided to the rotary control ring 20, although not shown in the figure. The position of these graduations and the indicator may be switched between the cover 70 and the rotary control ring 20, or a structure may be employed that allows the movement position of the sliding piece 30 to be seen directly.
The adjustment spring indicated by the number 80 in FIG. 4 is used to adjust the balance of forces exerted on the sliding piece 30, which is under the action of tension from the relay cable 40 and the inner cable 2a.
While the above is a description of various embodiments of the present invention, further modifications may be employed without departing from the spirit and scope of the present invention. For example, the base member 110 shown in FIG. 9 is formed with the axis Y that determines the extension direction of the guide groove 111 thereof being concentric with the axis X of the base member 110, and the guide path thereof is not in a spiral as in the above practical example, but rather in the form of an arc. With this structure, the control cable-use nozzle 113 also extends straight in the diameter direction. Such a base member 110 is particularly advantageous in cases in which the shifting control device is arranged in a position in which it is favorable for the control cable 2 to extend at a right angle to the axis X of the base member 110. Naturally, a change in the configuration of the guide groove must be accompanied by a change in the shape of the modified piece 30 as well, and in the case of an arc-shaped guide groove, the modified piece should be in the form of a partial ring.
Since this construction is employed, the displacement transmission mechanism can be positioned in a ring-shaped space, so the overall structure of the control device 1 is compact. An advantage here is that since the guide groove 11 has a guide surface that extends in the circumferential direction having an axis Y, even if the travel of the deflection means 30 is lengthened in order to increase the stroke by which the control cable 2 is displaced, the cylindrical control device 1 will remain virtually the same size overall because the guide groove that is used for this lengthening extends around the outside surface of the base member 10. If the axis Y that determines the extension direction of the guide groove 11 coincides with the axis X of the base member, then the movement locus of the deflection means 30 will be circular, which facilitates the production of the guide groove and the deflection means 30 that is applied to this guide groove. If the axis Y that determines the extension direction of the guide groove 11 is slanted with respect to the axis X of the base member, that is, if the guide groove is formed such that it extends in a spiral around the outside surface of the base member, then a longer guide path can be obtained with an outside surface of the same diameter, and this will also be preferable in cases in which the direction that the control cable 2 extends from the deflection means 30 must be at a right angle to the axis of the base member.
In the above embodiments, the control member 20 was formed as a complete ring that was fitted and rotated around the outside surface of the base member 10, but it may also be a partial ring that moves along the guide path formed in the base member 10. It is also possible to employ a configuration involving an ergonomic approach in which the rotational axis of the control member 20 is slanted with respect to the axis X of the base member, and the rotational control displacement is made to mirror the movement of the thumb as much as possible. If needed, it is also possible to employ a configuration involving a sliding tab that slides along a linear guide path.
The described embodiments involved a configuration in which a curved opening 31 was provided as a through hole to the sliding piece as the deflection means 30, and the extension direction of the relay cable 40 was changed by about 90 degrees by winding with this relay cable 40 inserted into said hole, but in order to eliminate the problem of friction between the relay cable 40 and the curved surface 31a, as shown in FIG. 9, it is also possible for a small pulley 131 to be rotatably provided to the sliding piece 130, and for the sliding piece to serve as the running block itself. An angle of 120 to 180 degrees is favorable for the extension direction of the relay cable changed by the deflection means. This is because exceeding 180 degrees will not usually produce any further benefit in terms of operating effort, and an angle under 120 degrees will not only diminish the obtained benefits in terms of operating effort, but will sometimes result in the overall device being longer in the axial direction. Of course, other embodiments may support different angles of deflection.
The first linking means 50 that fixes the relay cable 40 to the base member 10 can be very simple if it is made up of a through hole provided to the base member and a nipple 15 that prevents slippage of the relay cable 40 inserted in said hole, but the fixing of the relay cable 40 does not necessarily have to be to the base member, and the same function will be fulfilled if this fixing is to a structural member of the bicycle to which the base member is fixed, and such a structure is also within the scope of the present invention.
The above described embodiments represented a shifting control device that involved the use of the principle diagram shown in FIG. 2a, that is, a single running block. However, a shifting control device that involves the use of the principle diagram shown in FIG. 2b, that is, a plurality of running blocks (two in this figure), can also be structured similarly. For example, in the case of two running blocks, two guide grooves 11 are provided side by side to the base member 10, one end of the relay cable that is wound around the sliding piece 30 that slides through the first guide groove 11 is fixed to the base member 10, while the other end is fixed to a second sliding piece 30a that slides through a second guide groove 11, and one end of the relay cable 40 that is wound around the second sliding piece 30a is fixed to the base member 10, while the other end is fixed to the control member 20. As a result the operating effort required by the control member 20 is even lighter. To produce a shifting control device that uses even more running blocks, the number of guide grooves, sliding pieces, and relay cables is similarly increased, with the components being similarly connected in succession.
Thus, the scope of the invention should not be limited by the specific structures disclosed. Instead, the true scope of the invention should be determined by the following claims. Of course, although labelling symbols are used in the claims in order to facilitate reference to the figures, the present invention is not intended to be limited to the constructions in the appended figures by such labelling.
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A bicycle control device wherein a base member is provided for attachment to a structural member of the bicycle, and a control member is mounted for movement relative to the base member. A relay cable has a first end secured relative to the base member and a second end secured relative to the control member so that movement of the control member relative to the base member causes the first end of the cable to move relative to the second end of the cable. A linking member is disposed between the first end of the cable and the second end of the cable for movement with the cable. The linking member has an attachment location for attaching a control element of the bicycle to the linking member. The device may then operate according to the principle of a ruunning block.
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BACKGROUND OF THE INVENTION
1. Industrial Field
The present invention relates to electron beam lithography for use in producing large scale integrated circuits (LSIs), and is particularly applicable to a high-throughput electron beam lithography system and method capable of improving productivity while accomplishing a fine patterning ability.
2. Description of the Prior Art
LSI patterns are being formed in smaller, finer sizes and at higher degrees of integration than ever before, and it is further desired to realize patterning even finer than the resolution limit of light lithography employed thus far. Lithography that can satisfy this fine patterning desire has been achieved by electron beam lithography technology. However, known electron beam lithography technology has suffered from the problems of slow processing speed and poor productivity. One known technique for improving the productivity of such lithography technology, to obtain a higher throughput, is described in Japanese Patent Laid-Open No. 29981/1979, entitled "Electron Beam Irradiation Apparatus".
The basic concept of a high-throughput lithography method can be simply described by comparison with a conventional electron beam lithography method. FIG. 4 illustrates a lithography system and method based on a variable shaped technique which is a conventional electron beam lithography method. According to this lithography method, an electron beam 13 emitted like a shower from a gun 4 is shaped into a square form through a first aperture 5 having a square hole, and a square shaped beam 13' is focused on a second aperture plate 8' using a first lens 6 and a shaping deflector 7. The electron beam is formed into a square beam of any size by the second aperture plate 8' by adjusting the overlapping of the electron beam 13' and a square opening 14". A square shaped beam 13" that is formed is reduction-projected onto a predetermined position on a sample 12 while maintaining a precise focusing through a projection lens 9, a static deflector 10, and an objective lens 11. According to this conventional variable shaped lithography method, the pattern to be delineated is divided into squares of dissimilar sizes which are then delineated one by one. With the conventional method, therefore, even those patterns that are much repeated as shown, for example, on the sample 12 of FIG. 4 are all delineated by the same method. Accordingly, this conventional method requires a great number of beam "shots" and an extended period of time for lithography processing.
One way to improve the throughput is shown in FIG. 3, where desired lithography pattern elements 14' are formed in the second aperture plate 8 in advance. The electron beam 13' is shaped into pattern elements 14' and the pattern is delineated by repeating the cell projection of the thus shaped electron beams. The above lithography method makes it possible to greatly decrease the number of shots and to shorten the time for lithography processing. It is particularly effective for delineating memory LSIs such as DRAMs in which most of the patterns have periodicity, and makes it possible to increase the processing speed.
PROBLEMS TO BE SOLVED BY THE INVENTION
Despite a striking increase in the processing speed, however, the above aperture plate pattern lithography method still suffers from a serious problem. That is, proximity effects which are a problem specific to electron beam lithography.
This problem is best explained in detail with reference to FIGS. 2, 5 and 7. First, FIG. 7(a) illustrates electron beam lithography which desires to maintain a pattern gap l 3 on a resist film 20 on a silicon single crystalline substrate 19 using an electron beam 13". A conductive underlayer 21, typically tungsten or aluminum, is interposed between the substrate and the resist film. The incident electrons from the beam are scattered in the resist film 20 and in the silicon substrate 19, and lose energy. Scattering occurs both in a forward and backward direction. Forward scattering results from dispersion through the resist film, while back scattering results from electron reflection from the conductive underlayer 21. Back scattering is typically a much larger component of the overall scattering, and increases when a heavier material underlayer is used, such as tungsten as opposed to aluminum. Therefore, energy is stored even in the regions that are not directly irradiated with the electron beam 13". To more fully understand the proximity effect the following relationship must be known. When the position of an incident beam is denoted by y, the amount of energy stored at the position x is expressed as,
E(x)=∫∫yε·F(||x-y|.vertline.)d.sup.2 y
where F(γ)=c 1 ·exp[-(γ/δ 1 ) 2 ]+c 2 ·exp[-(γ/δ 2 ) 2 ]. The first term ("c 1 ") represents forward scattering in the sample, and the second term ("c 2 ") represents the effect of back scattering. Symbols c 1 , c 2 , δ 1 and δ 2 denote constants determined by the resist material, thickness of the resist film, underlayer material, and electron beam accelerating voltage. For example, at a beam energy of 30 kV, for a plain silicon wafer with no underlayer c 1 is 2.73×10 8 and c 2 is 4.46×10 5 , while with a tungsten underlayer the values are c 1 =2.77×10 8 and c 2 =1.75×10 6 . FIG. 7(b) shows a distribution of energy storage amounts in the resist film 20 in accordance with the above relationship. In the resist film 20 irradiated with the electron beam, the stored amount of energy gradually decreases from near the silicon tungsten layer 21 toward the surface of the resist. Here, the lines of the same kinds represent portions where the stored amounts of energy are equivalent. In the case shown in FIG. 7(b), when it is intended to form a pattern without dissolution, the resist film of the electron beam lithography region must be developed such that the stored amount of energy whose distribution is indicated by a solid line will assume a threshold level. Curves of a dot-dash chain line and a dotted line shown in the non-irradiated region of FIG. 7(b) represent the stored amounts of energy in the non-irradiated region in the case when the stored amounts of energy are greater than the above threshold level. Therefore, a pattern is formed in the non-irradiated region too. This is the proximity effect which noticeably appears as the figures of the circuit pattern are brought closer to each other and which is inherent in electron beam lithography.
With particular reference to FIG. 2, repetitive patterns of a high density are shown to be formed by using an electron beam resist film. According to the conventional lithography method, the figures are delineated one by one. In order to avoid the proximity effect, therefore, the electron beam irradiation amount is finely adjusted during the lithography or the individual delineated figures are finely adjusted in order to decrease the storage of energy for the non-irradiated regions as shown above. When the above repetitive patterns are to be delineated by the cell projection method, however, an aperture pattern opening 14' (FIG. 3) in the second aperture 8 corresponding to the pattern elements 3 can be formed by one time of exposure by the lithography system that is shown in FIG. 3. When the projection is effected at one time by using the desired pattern opening 15 as is shown in FIG. 5, those portions not irradiated with the electron beam, but which are close to each other, after developing can undergo dissolution due to the pattern proximity effect. A resist pattern is then formed as shown in FIG. 6. Therefore, when etching patterns that tend to have strong proximity effects, such as the high-density patterns that are to be formed by the cell projection method, a serious problem exists because it becomes very difficult to form the patterns as desired.
The present invention provides a new and improved system and method of electron beam lithography that can employ a pattern opening and yet overcome the problems of proximity effects.
BRIEF SUMMARY OF THE INVENTION
In accordance with the present invention an electron beam lithography method and system are provided for projecting a desired preselected pattern of elements onto a wafer for production of integrated circuits thereon, wherein the system is particularly useful for compensating for proximity effects between selected adjacent portions of the preselected pattern of elements. An electron beam emits a shower onto the wafer that is focussed by a lens and aperture plate into a predetermined beam pattern corresponding to the preselected pattern of elements. The aperture plate includes a mask having a plurality of first portions corresponding to first element portions relatively spaced for avoiding proximity effects between elements on the wafer, and a plurality of second portions corresponding to second element portions relatively spaced for obtaining proximity effects between elements on the wafer, wherein the plurality of mask second portions are sized to have an increased adjacent spacing relative to resultant adjacent spacing of the corresponding second element portions, whereby the resultant adjacent spacing of the second element portions on the wafer is selectively reduced by the proximity effects.
The method and system is provided to estimate by simulation the undesirable dissolution of resist film caused by proximity effects in a pattern made with electron beam lithography, and adjustment of pattern sizing to maintain pattern element separation with minimum spacing. The method comprises calculation of stored energy due to forward and back scattering at selected points in the resist film that separate the delineated pattern. Where the stored energy at some of the selected points is determined to exceed the level that will substantially dissolve the resist film, adjacent pattern elements are adjusted in size in a pattern mask by an amount necessary to maintain sufficient resist film at those points. Pattern elements which are adjacent points where the stored energy is estimated to be too low to be sufficient to dissolve the resist are not adjusted.
In accordance with another feature of the invention, a fine wire mesh is included in the mask over only selected portions of the pattern elements to reduce the transmission density of the electron beam at those portions.
It is an object and benefit of the present invention that an electronic beam lithographic technique can be employed for a highly dense, periodically repeated cell pattern that compensates for resist film dissoluting due to proximity effects.
It is another object and benefit that pattern correction is achieved by adjusting only selected portions of the cell pattern that are estimated to have undesirable resist film dissolution.
It is yet another object and benefit that a repetitive and dense pattern can be delineated precisely and quickly by the simultaneous projection of a plurality of cells of the pattern for enhanced practicability and higher throughput.
Other benefits and advantages of the invention will become apparent to those skilled in the art upon a reading and understanding of this specification.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram illustrating different embodiments of mask cell patterns for an electron beam lithography system made in accordance with the present invention, wherein FIG. 1(A) shows a delineated pattern of a first embodiment, FIG. 1(B) shows the delineated pattern of a second embodiment, and FIG. 1(C) shows the delineated pattern of a third embodiment;
FIG. 2 is a schematic diagram showing an example of a projected periodic pattern that may be obtained in accordance with the above embodiments;
FIG. 3 is a schematic perspective view of a cell pattern projection assembly using an electron beam lithographic technique in accordance with the invention;
FIG. 4 is a schematic perspective view of a prior art electron beam lithography assembly;
FIG. 5 is a view of a portion of a conventional cell pattern mask;
FIG. 6 is a view of a projected cell pattern that may be obtained with the mask of FIG. 5;
FIG. 7(A) is a drawing illustrating the application of beam energy to a resist film when a high-density cell pattern is being delineated;
FIG. 7(B) shows a distribution of the amounts of energy stored in the resist film of FIG. 7(A);
FIG. 8 is a diagram showing resist sensitivity characteristics;
FIG. 9 is a schematic diagram showing a cell projection having the desired delineated figures and selected points for calculating the amounts of energy stored;
FIG. 10 is a schematic diagram showing a similar cell projection but adjusted in conformance with the invention and the selected points for calculating the amounts of energy stored;
FIG. 11 is a graph showing the relationship between stored energy in a resist film portion and the spacing between projected cell elements bordering the resist; and,
FIG. 12A is a graph showing the relationship between spacing of the elements in a mask and resulting spacing of projected cell elements on a Si wafer and FIGS. 12B and 12C show the spacing between mask apertures and resulting element spacings on the wafer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings where the showings are for purposes of illustrating preferred embodiments of the invention only and not for purposes of limitation, the FIGURES show an assembly and method useful for projection of a plurality of repetitive cell elements in an electron beam lithographic technique to obtain a highly dense pattern in a high throughput production method.
The over-all object of the invention is achieved by the electron beam lithography system which repeats the cell projection onto the surface of the wafer sample, where the system is provided in advance with means for correcting the proximity effects that develop among the repeated patterns on the surface of the sample. Specific steps for achieving this object will now be described in conjunction with FIGS. 9 and 10. First, what is shown in FIG. 9 is a part of a schematic diagram of a cell projection such as may be used in the mask pattern 14' (FIG. 3) for the desired preselected pattern of circuit elements corresponding to a delineated pattern of resist on the wafer. Here, symbols l 1 , l 2 , l 3 , m 1 and m 2 in the drawings represent sizes of the delineated patterns indicated by the portions of crossing lines. Further, the points o 16 and points * 17 in the drawings represent portions where it is estimated that the proximity effect is likely to take place on the wafer delineated patterns, and are used as sampling points for calculating the stored amounts of energy. Using these sampling points, distribution of the amounts of energy stored in the resist film is found by simulation in the same manner as described above in detail, and the proximity effects among the patterns is estimated. It is found that the energy is not stored at the points * 17 in such amounts that affect the formation of the resist pattern but a resist pattern that is not expected is formed at the points o 16. In other words, first element portions 30 are determined to be relatively spaced for avoiding proximity effects between resist elements on the wafer when the stored energy is calculated for the points * 17, while second element portions 31 are calculated to obtain sufficient stored energy between them at points o 16 so that the proximity effects will affect the desired resist pattern.
It was therefore determined to form an adjusted resist mask pattern and simulate by calculation the stored energy when part of the mask portion is removed as shown in FIG. 10, and it was found that the resist pattern for the corresponding elements on the wafer could be formed as desired at the sampling points ⊚ 18 by the pattern proximity effects, but without permitting the formation of the resist pattern at the sampling points o 16. That is, the mark aperture 1 for shaping the electron beam for cell transfer to the wafer is formed in a shape as shown in FIG. 1(a), so that the delineated pattern 1, from which the figure of a size l 4 × m 1 (FIG. 10) is removed in advance, is projected at one time. Here, the portions 2 shown by a broken line are the portions of the delineated figures removed for correcting the proximity effect. Thus, the aperture for focussing the beam is set so that first portions 30 remain unadjusted for proximity effects while second portions 31' (FIG. 10) are sized to have an increased adjacent spacing relative to what the resultant adjacent spacing of corresponding second element portions of resist 31 (FIG. 9) will be due to proximity effects.
Alternatively, the resist film portion that is estimated to easily develop proximity effect among the delineated patterns during the lithography can be adjusted by substantially decreasing the current density of the delineating irradiated electron beam for partly decreasing the amount of energy that is stored in that portion. As shown in FIG. 1B, for instance, a mesh 2' composed of fine wires having a size smaller than the resolution limit is provided at selected aperture portions that are expected to easily develop proximity effects among the delineated patterns. This method also makes it possible to selectively correct for proximity effects and to form the resist pattern as desired like the aforementioned case.
Furthermore, as another alternative, the proximity effect can be corrected even more precisely by combining the removal of the appropriate portions of the pattern figures with the adjustment in the effective current density by the addition of the absorbing mesh as shown in FIG. 1C.
The detailed embodiments of the present invention will now be described in conjunction with the drawings.
First Embodiment
This embodiment has a mask aperture equipped with a shaped pattern as shown in FIG. 1A in order to form a resist pattern that is shown in FIG. 2. The lithography system used for the lithography has the following specifications: an acceleration voltage of electron beam of 30 kV and a current density of 5 A/cm 2 . Further, a negative resist RD-2000N (produced by Hitachi Kasei Co.) having a thickness of 0.5 μm is used as a resist film for forming a pattern on the wafer silicon substrate. The patterns are formed by the resist film using an alkali developing solution. FIG. 8 shows electron ray sensitivity characteristics of the resist film under the above-mentioned conditions. From FIG. 8, the resist pattern is formed with the shaped electron beam irradiation amount of 40 μC/cm 2 . When the electron beam irradiation amount is smaller than 14 μC/cm 2 , the resist is all dissolved by developing.
FIG. 9 shows a portion of the desired delineated pattern. The pattern size is so defined that l 1 =0.4 μm, l 2 =0.6 μm, l 3 =0.4 μm, m 1 =1.2 μm, and m 2 =1.2 μm. By taking the above lithography conditions into consideration, the anticipated amount of electric charge stored in the resist film when the pattern is delineated is found by calculation as discussed above. Points o 16 and points * 17 represent the portions where it is estimated that proximity effects easily takes place among the delineated patterns, and are used as calculation sampling points. As a result of the simulation, the amounts of energy stored at the sampling points o 16 and sampling points * 17 are found to be 30 μC/cm 2 and 12 μC/cm 2 , respectively. From FIG. 8, it is estimated that the resist film is left by more than 90% of its thickness at the sampling points o 16 causing the pattern to be coupled together (FIG. 6), but the resist film is extinguished as desired at the sampling points * 17.
According to the present invention, therefore, portions 31' (FIG. 10) of the mask aperture are deformed as shown in FIG. 1 by reducing the sizing of the portions by the dimensions 2 so that the delineated pattern (FIG. 10) obtained by removing the region l 4 ×m 1 (where l 4 =0.2 μm, m 1 =1.2 μm) from the delineated pattern of FIG. 9 can be projected at one time according to the present invention. The aperture plate consists of a semiconductor single crystalline plate. In this embodiment, however, the patterning is effected by the customary method using a silicon single crystalline plate in order to form the pattern opening while maintaining high precision. In this case, it is confirmed by simulation that the amounts of energy stored at the sampling points o 16, * 17 and ⊚ 18 shown in FIG. 10 are 12 μC/cm 2 , 12 μC/cm 2 and 30 μC/cm 2 , respectively. In the practical formation of the resist pattern on the silicon single crystalline substrate, the high-density pattern as shown in FIG. 2 could be correctly formed maintaining a dimensional error of smaller than 9%.
FIGS. 11 and 12 more particularly illustrate the relationships between stored energy and the necessary aperture spacings to obtain the desired resist spacings on the wafer. FIG. 11 shows the stored energy imparted by a 30 Kv beam on either a silicon wafer or one including the tungsten layer. The graph will of course change according to beam intensity. For silicon only the pattern spacing must be at least 0.7 μm, and for silicon and tungsten the pattern spacing must be at least 0.9 μm to avoid the stored energy in the resist in the spacing receiving enough stored energy from proximity effects to exceed the dissolved limit. In FIG. 12A this relationship is further illustrated relative to the desired resist spacing where it is shown that for desired resist spacings of less than 1.4 μm on a tungsten underlayer wafer the spacing between aperture patterns must be increased relative to the resist spacing. For such cases, FIG. 12B shows that the spacing between aperture patterns S1 will be greater than the resist spacing S2 (FIG. 12C) on the wafer.
Second Embodiment
Next, another embodiment of the electron beam lithography system of the present invention will be described in conjunction with FIG. 1B. Here, however, the specifications of the lithography system, the delineating and developing conditions such as the resist and developing solution, and the desired delineated pattern are the same as those of the aforementioned first embodiment.
In this embodiment as shown in FIG. 1B, a mesh 2' consisting of wires finer than a beam resolution limit is provided at selected portions of the aperture where it is expected that the proximity effects will occur among the patterns during the lithography. The fine wire used for the mesh 2' is a gold wire having a width of 2 μm. The contraction rate of the lithography system is 1/25, and it is confirmed that the metal wire pattern does not resolve when the resist pattern is being formed. In the opening fitted with the mesh 2', the density of the fine wire is so adjusted that the transmission density of the electron beam is decreased by 30%. The delineated pattern at this moment is shown in FIG. 9. It is confirmed by simulation that the amounts of energy stored at the sampling points o 16 and * 17 are 10 μC/cm 2 and 10 μC/cm 2 , respectively. Even when the resist pattern is practically formed on the silicon single crystalline substrate, the high-density pattern shown in FIG. 2 can be highly precisely formed maintaining a dimensional error of smaller than 8% like in the first embodiment. It is a feature of this second embodiment that only selected portions of the mask aperture are provided with the mesh. These portions are determined according to the simulation calculations as identified in the practice of the first embodiment.
Third Embodiment
Next, a further embodiment of the electron beam lithography system according to the present invention will be described as a third embodiment in conjunction with FIG. 1C. The specifications of the lithography system, the delineating and developing conditions such as the resist and developing solution, and the desired delineated pattern are the same as those of the aforementioned embodiments.
In this embodiment, the aperture is deformed as shown in FIG. 1 based on the delineated pattern that is shown in FIG. 9, in order to project at one time the delineated pattern, shown in FIG. 10 that is obtained by removing the region l4×m 1 (where l4=0.2 μm and m 1 =1.2 μm) from the aperture where it is estimated that the proximity effects will occur among the patterns during the lithography. Furthermore, the deformed opening is also provided with a mesh 2' made of wires finer than the resolution. In the third embodiment shown in FIG. 1C, the fine wire used for the mesh 2' is a gold wire having a width of 2 μm. In this embodiment, the contraction rate of the lithography system is 1/25, and it has been confirmed that the gold wire pattern does not resolve when the resist pattern is being formed. In the opening fitted with the mesh, the density of the fine wire is so adjusted that the transmission density of the electron beam is decreased by 20%.
The delineated pattern at this moment is shown in FIG. 10. It is confirmed by simulation that the amounts of energy stored at the sampling points o 16, * 17 and ⊚ 18 are 5 μC/cm 2 , 5 μC/cm 2 and 25 μC/cm 2 , respectively. Even when the resist pattern is practically formed on the silicon single crystalline substrate, the high-density pattern shown in FIG. 2 can be highly precisely formed maintaining a dimensional error of smaller than 5% like in the aforementioned embodiments.
According to the electron beam lithography system of the present invention which repeats the cell transfer using the electron beam formed into any shape as described in the foregoing, provision is made for correcting the proximity effect that develops among the patterns. Therefore, when the individual patterns that are highly densely and periodically repeated, are to be delineated, a desired pattern can be delineated at high speeds maintaining high precision using the lithography system which is based on the very effective cell projection method and the lithography method. It is therefore made possible to greatly enhance the practicability of the electron beam lithography system and the lithography method.
The second aperture fitted to the lithography system of the present invention is chiefly composed of a semiconductor single crystal and, particularly, a single silicon crystal, enabling the pattern opening to be machined with high precision.
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A system and method are provided for compensating for proximity effects between selected adjacent portions of pattern elements on an integrated circuit wafer where it is determined by simulation that undesirable resist patterns will result. The subject lithography system includes projecting an electron beam onto the wafer through an aperture plate of pattern elements to obtain the desired beam pattern. An aperture mask includes a plurality of first portions corresponding to first wafer circuit element portions spaced for avoiding proximity effects on the wafer and a plurality of second portions corresponding to second element portions spaced for obtaining proximity effects between elements on the wafer. The plurality of second portions are sized to have an increased adjacent spacing relative to a resultant adjacent spacing of the corresponding second element portions whereby the resultant adjacent spacing of the second element portions on the wafer is selectively reduced by the proximity effects. Alternatively, or in addition, a wire mesh is provided at the second portions of the aperture plate to reduce the beam intensity for corresponding reduction of the proximity effects.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This Nonprovisional Application for Patent incorporates by reference (to the extent it does not conflict with the disclosure herein) and claims the benefit and priority of pending Provisional Application having Ser. No. 61/010,168 filed Jan. 4, 2008 entitled “Cylinder Anti-Roll/Slide Device,” commonly owned with the instant Application.
COPYRIGHT NOTICE
[0002] A portion of the disclosure of this Patent document, including the drawings and Appendices, contain material which is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the Patent document or the Patent disclosure as it appears in the Patent and Trademark Office Patent files or records, but otherwise reserves all copyright rights whatsoever.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] Versions and embodiments of the present invention relate generally to devices for cylinders. More particularly, versions of the invention relate to cylinders used to contain gases under pressure. Specifically, a version of the invention relates to a scuba tank cylinder (air tank) anti-roll and/or anti-slide safety device and new, useful and unobvious versions thereof.
[0005] 2. Description of the Related Art
[0006] As is well understood by one skilled in the art, for many years the traditional method for transporting scuba tanks (and other similar type tanks) in cars, truck, boats and other vehicles has been to simply stack them next to each other and/or put towels between the scuba tanks to prevent them from rolling and/or hitting each other. For instance, sometimes scuba tanks are transported in the bed of a pick-up truck or trunk of a car, especially for recreation scuba divers that are not professionals. The traditional transportation device (or lack thereof) has disadvantages, especially when in moving vehicles that may make emergency stops from hitting the brakes to avoid a collision or involved in a crash with a stationary object or other vehicle. First of all, the heavy tanks (usually made of steel or aluminum) become flying projectiles from the pick-up truck bed or trunk of a car that may cause damage and/or injuries to the occupants.
[0007] Secondly, these tanks have valves attached to the top to allow the compressed air (or other gases) to be dispersed in a controlled manner; if a transportation accident causes this valve to be severed from the tank, the rapidly escaping gas essentially makes the tank act as a rocket with potential deadly consequences. Additionally, the tanks may bump and/or collide with each other in the vehicle while moving, causing cosmetic blemishes on the tanks.
[0008] What is needed today for safe transportation of cylinders in moving vehicles is a anti-roll/anti-skid device to prevent rolling, sliding and/or bumping of the cylinders either alone or among multiple tanks. This new, useful and unobvious “Cylinder Anti-Roll/Slide Safety Device” solves this need. Versions of the invention utilize a band that is placed around the tank(s).
SUMMARY OF THE INVENTION
[0009] The present versions of the invention address at least one, some or all of the above-referenced needs in the art by providing new, useful and unobvious devices in versions of the invention for anti-roll and anti-slide features for use with cylinders.
[0010] The preferred embodiment of the invention utilizes soft, flexible rubber or rubber-like material. Other embodiments may use rigid, semi-rigid and/or flexible materials of various elasticity, depending on the user's desires, need or type use.
[0011] Benefits, features and problems solved by versions of the invention include these objects/advantages: It is an object and/or advantage of versions of the invention to prevent the scuba tanks form bumping (the device may also be called a “tank bumper”) and banging into one another. Another object and/or advantage is to allow versions to use soft rubber that makes the article a non-slip product that serves as a anti-slip device. Another object and/or advantage is to allow versions of the invention to have at least one foot molded into an elastic band of suitable width, length and thickness that prevents the tank form rolling on any flat surface. Another object and/or advantage is in other versions the feet also serve to hold the tank next to it from rolling and interlocks a row of tanks together. Another object and/or advantage is to allow versions of the band to protect the tank from being damaged or chipped. Another object and/or advantage is to allow versions of the tank bumper to be thin enough as to not interfere in the strapping of the tank on to the buoyancy compensator. Another object and/or advantage is to allow versions of the band to hold and fit flush on to the back pack or buoyancy compensator flat by having the feet lie flat against the back pack. Another object and/or advantage is to allow versions to use soft non slip rubber prevent the tanks from sliding in the bed of a pickup truck. Rolling is prevented due to the lateral movement but the soft rubber prevents slipping of the tank along the length of the longitudinal axis. Another object and/or advantage of versions of the invention is it prevents the buoyancy compensator form slipping from the holder when used with scuba gear. At least one object and/or advantage is accomplished by at least one, some or all versions of the present invention.
[0012] The foregoing objects, benefits and advantages of versions of the invention are illustrative of those which can be addressed by versions of the invention and not intended to be limiting or exhaustive of the possible advantages that can be realized. These and other advantages will be apparent from the description herein or can be learned from practicing versions of the invention, both as embodied herein as examples or as modified in view of any variations which may be apparent to those of ordinary skill in the art. Therefore, the invention resides in the novel devices, methods, arrangements, systems, combinations and improvements herein shown and described as examples and not limited therein.
[0013] It is understood that the versions of the inventions are new methods, devices and systems for cylinder anti-roll/anti-slide safety.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] In the manner in which the above-recited and other advantages and objects 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 to be 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:
[0015] FIG. 1 is a section view of a version of the invention.
[0016] FIG. 2 is a partial section bottom view of another embodiment of the invention and releasably attached feet.
[0017] FIG. 3 is a bottom view of an embodiment of the invention.
[0018] FIG. 4 is a perspective view of an embodiment of the invention.
[0019] FIG. 5 is a perspective view of an embodiment of the invention.
[0020] FIG. 6 is a perspective view of an embodiment of the invention.
[0021] FIG. 7 is a section view of an embodiment of the invention.
[0022] While the present invention will be described with reference to the details of the embodiments of the invention shown in the drawings (and some embodiments not shown in the drawings), these details are not intended to limit the scope of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0023] The core of the version of the preferred embodiment of the invention is depicted in FIG. 4 . The dimensions shown are for illustration and example only, as the device is scalable to any desired and/or suitable size.
[0024] It is also understood that whenever and/or is used in this patent application it means any combination or permutation of all, one, some, a plurality or none of each of the item or list mentioned, which is not intended to be limiting but merely for example and illustration. It is also understood that (s) designates either singular or plural. It is also understood that that “or” is an inclusive “or” to include all items in a list and not intended to be limiting and means any combination or permutation of all, one, some, a plurality or none of each of the item or list mentioned. It is also understood that “including” means “including but not limited to” any combination or permutation of all, one, some, a plurality or none of each of the item or list mentioned.
[0025] The apparatus of the invention is conveniently fabricated in the preferred embodiment by conventional and standard methods of forming, molding, injecting, heating, pressurizing, releasing and finishing in the rubber and plastic fabrication and injection molding arts using conventional and standard materials.
[0026] For example, versions of the invention and incorporated components may be fabricated from aluminum, steel or other like metals or any other suitable material as will be readily apparent to one of ordinary skill in the art. The present invention (or components of) may also be fabricated in best mode from non-metallic materials for lighter weight, reduced cost and resistance to corrosion. These non-metallic materials include, among others, conventional polymers such as, for example, polystyrene, polycarbonate, polyurethane, polyethylene, phenol formaldehyde resins, polybutylene, Teflon and the like.
[0027] Plastics (any one of a large and varied group of materials consisting wholly or in part of combinations of carbon with hydrogen, oxygen, nitrogen and other organic and inorganic elements; while solid in the finished state, at some stage in its manufacture, it is made liquid, and thus capable of being formed into various shapes, usually through the application of heat and/or pressure), such as monomer (one unit—the building block for polymer molecules) or polymer (many monomer units strung together to make long molecules) used in polymerization (the process of combining short molecules to make long molecules) may be used.
[0028] Thermoplastics (plastics that can be repeatedly softened and hardened by heating and cooling) as well as Thermosets (plastics that are cross-linked during polymerization and cannot be softened without degrading some linkages) may also be used.
[0029] Thermoplastic resin types such as crystalline (thermoplastics containing areas of dense molecular alignments known as crystallinity), amorphous (thermoplastics with no crystallinity in the solid state), liquid crystal polymers (LCPs) (stiff, rod-like structures organized in large paralleled arrays in both melted and solid states) may also be used.
[0030] All components may be referenced in plural for convenience, as only at least one of all components are necessary, if desired, for proper operation and use in other embodiments. Ideally, all components (or some components) are injection molded from non-metallic materials (plastic and/or rubber, including natural and/or synthetic rubber and/or rubber-like compositions) as previously mentioned above.
[0031] The components may be attached, connected, linked, related, affixed, disposed on, integrated into, adjoined, combined, bonded, united, associated, joined, tied, secured, bound, rigidly attached, flexibly attached, attached with rotational freedom in at one least axis, and/or integrated onto each other as desired by the operator.
[0032] To make the invention in its preferred embodiment, one skilled in the art would assemble and/or fabricate, for example, the main component comprising an elastic band 1 . Then at least one foot 2 may be integrated into the band when fabricated (using molds) or releasably attached to the band via an attachment means 4 . The attachment means may be of any suitable type—loop, aperture, glue, sewn, webbing, fastener, screw, bolt, weld, connector link, grommet, snap, rivet, thread, rope, twine, rod, dowel, hook, plug, connector, and/or any other means, either attached/secured permanently, temporarily and/or releasably attached.
[0033] Another version may use apertures 3 or other connection means 3 for use with a cord to thread through the at least one foot of the device, as shown in FIG. 6 . The connection means may be of any suitable type—loop, aperture, glue, sewn, webbing, fastener, screw, bolt, weld, connector link, grommet, snap, rivet, thread, rope, twine, rod, dowel, hook, plug, connector, and/or any other means, either attached/secured permanently, temporarily and/or releasably attached.
[0034] For example, a hole drilled through the foot of the device in one version of the device allows extra products to be attached to the cylinders. This might be used in the case of needing extra spear shafts when using Hawaiian Slings, & or lineless spear shafts. The holes would be used as a spare holders for extra shafts if the diver loses the spear he shot at the fish, allowing the diver to maintain his dive with out surfacing to reclaim another spear shaft. 1 or 2 sears shafts can be carried and are out of the way located on the back of the cylinder.
[0035] Additionally, the holes (or other type attachment means) drilled into the foot allows a stretchable bungee to be secured between 2 or more versions of the device. This will allow the cylinders to be locked together either by using a insert-able interlocking device such as shown on the attachment or by using any device with hooks to lock and or stretch around the cylinder that can then be hooked into the holes. The cord or bungee that is hooked between the devices will hold the cylinders in place regardless where they are located. The cord can be hooked into the foot and then be locked to a stationary device such as the boat or dock. This means for interlocking 5 may comprise a bungee, cord, connector link, thread, rope, twine, rod, dowel, wire, connector, and/or any other means, either attached/secured permanently, temporarily and/or releasably attached.
[0036] To use the invention in this embodiment, particularly with a scuba tank, the operator would stretch and place/slide the device around the scuba tank (or any other type tank) from either the top or bottom end of the tank to the desired location. To remove the device, the above procedure would be reversed; grasp the band (or feet on the band) and stretch and place/slide the band off from the tank top or bottom.
[0037] The above-referenced lists, options, functions, instructions, applications, interactions, items, products, goods, groups and sub-groups are merely intended as illustration and examples, and are not intended by the inventor to in any way limit the addition, deletion or modification of any said lists, options, functions, instructions, commands, applications, interactions, items, products, goods, groups and sub-groups as might be desirable or useful to someone skilled in the art. All components of the above-mentioned system are well known in the art.
[0038] As will be apparent to persons skilled in the art, such as a person in the plastic and/or rubber injection molding industry, scuba gear designer, compressed gas tank designer or other similar-type individuals, various modifications and adaptations of the structure and method of use above-described will become readily apparent without departure from the spirit and scope of the invention, the scope of which is defined in the claims. Although the foregoing invention has been described in detail by way of illustration and example, it will be understood that the present invention is not limited to the particular description and specific embodiments described but may comprise any combination of the above elements and variations thereof, many of which will be obvious to those skilled in the art. Additionally, the acts and actions of fabricating, assembling, using, and maintaining the preferred embodiment of this invention is well known by those skilled in the art. The invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiment is therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the 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.
[0039] An article of manufacture for use with scuba tanks, comprising:
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An article of manufacture is disclosed comprising a circular or nearly circular elastic band of suitable diameter, length, depth and width, and at least one foot integrated onto the elastic band. Also disclosed is the foot releasably attached to said elastic band via a means for attaching. Also disclosed is the foot further comprising an aperture in said foot. Also disclosed is the foot further comprising a means for connecting in said foot. Also disclosed is a means for interlocking attached to the means for connecting in said foot, either permanently or releasably attached to said foot.
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CROSS REFERENCES TO RELATED APPLICATIONS
This application is a continuation of prior International Patent Application Number PCT/US2009/031306, filed Jan. 16, 2009, said international application hereby incorporated herein in its entirety and itself claiming benefit of and priority to U.S. Provisional Patent Application No. 61/021,505, filed 16 Jan., 2008, said provisional application also incorporated herein in its entirety.
BACKGROUND OF THE INVENTION
Generally, the inventive technology relates to the field of bar retention. More specifically, the inventive technology, in embodiments, relates to bar coupling sleeve apparatus (e.g., rebar coupling sleeve apparatus), bar end portion retainer apparatus and bar retention methods that may find particular application in, e.g., the reinforced structure construction industry.
BACKGROUND ART
In reinforced concrete construction, including buildings, bridges, and other structures, reinforcing steel (e.g., rebar) is used to resist tensile and shear stresses. Since the concrete is relatively inefficient in resisting or withstanding such stresses, reinforcing steel is added where these stresses occur in a structure to significantly increase the overall strength of the structure. In addition to adding strength to a structure, reinforcing steel also enhances the ductility of the structure. In other words, it increases the structure's ability to absorb energy, which is a desirable characteristic for any structure that may be subject to, e.g., seismic forces.
In many structures, for the reinforcing steel to be effective, the reinforcing steel must “continuously” extend for a certain length, meaning that it must not have any discontinuities at any point along that given length. If this length is greater than the length of a bar that can reasonably be placed into position, the reinforcing steel bar must be “spliced” (or connected end-to-end) with another length of reinforcing steel bar. Typically, this splice is created by lapping the two reinforcing bars creating a “lap splice.” The length of the overlap of the lap splice is governed by commonly accepted codes and standards and depends on numerous factors including, but not limited to, reinforcing bar diameter, grade of reinforcing bar, compressive strength of concrete, concrete cover. The most common standard in the US, from which many codes are formed, is “Building Code Requirements for Structural Concrete” by the American Concrete Institute (ACI), more commonly know as ACI 318 . ACI 318 provides for three types of splices—lap splices, mechanical splices, and welded splices. ACI 318 requires mechanical and welded splices—in addition to lap splices—to be capable of withstanding, in tension or compression, a design force such as 125% of the force that would cause a stress equal to the yield strength of the spliced reinforcing bar. The device of the inventive technology falls into the category of a mechanical splice; it must have a design strength such that it can withstand, without failure, 125% of the yield strength of the reinforcing bar.
Another common occurrence in concrete construction is the need to terminate a reinforcing bar at a specific location in or at the end of the structure. Often the entire strength of the reinforcing bar is required a short distance from the end of the bar. However, because forces are transferred from the reinforcing bar to the concrete primarily by the mechanical keying of the reinforcing bar deformations, a certain length of bar, and therefore a certain number of deformations, is required to develop the full strength of the bar. ACI 318 refers to the length as the “development length” of the bar. When the development length of the bar exceeds the distance from the end of the bar to the point where the full strength of the bar is required, special provisions must be employed to shorten the development length of the bar. Typically, this is done by creating a bend, or hook, in the reinforcing bar. Another viable option is to use a mechanical anchor, which is typically flanged to engage more concrete and which can develop 125% of the capacity of the bar at a point where such strength is needed. Without such provisions, adequate strengths are not observed at all locations needed. Particular embodiments of the inventive technology, such as those depicted in FIG. 2 , are able to provide code strengths (design strength) at such “terminal” locations.
BRIEF SUMMARY OF THE INVENTION
Preferred embodiments of the inventive technology provide a device—a contiguity—may, in embodiments, be described as a simple high-strength steel sleeve with holes at each end and that continue towards the longitudinal center of the cylinder, defining chambers. The inner surface of the chambers can be deformed (in at least one embodiment, they may be concentrically deformed, in another, helically deformed). In preferred embodiments, the smallest diameter of the chambers, occurring at the top of the deformations (e.g., the most intra-radial portion of the deformations), may be slightly larger than the diameter of the reinforcing bar. An adhesive (a non-cementitious material) may be placed into one of the holes and, thereafter, the reinforcing bar may be inserted into the hole, thereby forcing the adhesive into the valleys formed by the deformations of the device. As is the case with other reinforcement splices, two important functionalities of the inventive technology are the transfer of tensile forces from one deformed reinforcing bar to the other, and the transfer of compressive forces from one deformed reinforcing bar to the other.
In embodiments with deformations of the inner surface of the contiguity, such deformations may serve several functions. First, the deformations (in particular their size relative to the reinforcing bar and the gap formed thereby) may be sized to provide passages through which the adhesive can flow to surround the entire reinforcing bar. Such, as an ancillary functionality, increases the surface area of the bar that is in contact with the adhesive, allowing more bonding between the adhesive and the reinforcing bar. Additionally, the deformations provide a mechanical anchorage for the adhesive. The deformations mechanically engage the adhesive to resist the tendency of the adhesive to be withdrawn from the device when a tension force is applied to the reinforcing bar. As should be understood, in particular embodiments of the inventive technology, deformations on the inner surface of the holes aid in force transfer through wedging action on the cured adhesive. It is also of note that no special tools are required for installation and that no special treatment of the deformed reinforcing bars is required for installation.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 shows a cross-sectional view of at least one embodiment of the inventive technology.
FIG. 2 shows a cross-sectional view of at least one embodiment of the inventive technology usable at the end of a concrete structure.
FIG. 3 shows a cross-sectional view of at least one embodiment of the inventive technology, in particular showing the forces observed in response to a tensile force applied to the bar, where such forces are applied by the deformations on the outside of reinforcing bar established inside the coupler, through cured adhesive to the deformations on the inside of an inventive coupler.
FIG. 4A shows a side view of at least one embodiment of the inventive technology in use coupling two bars.
FIG. 4B shows a cross-sectional side view of at least one embodiment of the inventive technology in use coupling two bars.
FIG. 5A shows a cross-sectional side view of at least one sleeve embodiment of the inventive technology.
FIG. 5B shows a cross-sectional side view of at least one single bar embodiment of the inventive technology.
FIG. 5C shows a side view of at least one sleeve embodiment of the inventive technology.
FIG. 5D shows a side view of at least one single bar embodiment of the inventive technology.
FIG. 6A shows a cross-sectional side view of a portion of the single or two bar apparatus, showing deformations as may be found in certain embodiments of the inventive technology. Of course, a myriad of other possible deformations may be used.
FIG. 6B shows a cross-sectional side view of a portion of the single or two bar apparatus, showing deformations as may be found in certain embodiments of the inventive technology.
DETAILED DESCRIPTION OF THE INVENTION
As mentioned earlier, the present invention includes a variety of aspects, which may be combined in different ways. The following descriptions are provided to list elements and describe some of the embodiments of the present invention. These elements are listed with initial embodiments, however it should be understood that they may be combined in any manner and in any number to create additional embodiments. The variously described examples and preferred embodiments should not be construed to limit the present invention to only the explicitly described systems, techniques, and applications. Further, this description should be understood to support and encompass descriptions and claims of all the various embodiments, systems, techniques, methods, devices, and applications with any number of the disclosed elements, with each element alone, and also with any and all various permutations and combinations of all elements in this or any subsequent application.
At least one embodiment of the inventive technology may be described as a bar coupling sleeve apparatus that comprises: a rigid contiguity 1 defining a longitudinal axis 6 , and having two ends 7 and an opening 9 at each the ends for reception of bar end portions (e.g., rebar end portions); a fluid impervious barrier 8 (through which, of course, fluid cannot pass) established as part of the contiguity to define an end of each of two fluidically non-communicative chambers 10 within the contiguity, each of the chambers sized to accommodate a different one of the bar end portions and a curable wet fluid (e.g., adhesive) 3 ; and two fluid outlet ports 4 , each associated with a different one of the chambers, and each enabling fluidic communication (the passage of a fluid such as air or adhesive) between its associated chamber and an environment external 20 of the contiguity. As in certain other embodiments, each of the two fluid outlet ports may enable fluidic communication between the environment and a barrier proximal end portion 21 of its associated chamber. Further, the curable wet fluid (e.g., adhesive such as epoxy), upon curing, retains the bar end portions in a different one of the chambers. Of course, fluid can not directly pass from one fluidically non-communicative chamber to the other (a theoretically possible passage of air from one chamber, out its associated fluid outlet port, out to the environment external of the contiguity, and then through a fluid port associated with a different chamber is not considered a type of fluidic communication that the term “fluidically non-communicative” excludes; the term primarily excludes any sort of fluid port through a barrier between the two chambers).
At least one embodiment of the inventive technology may be described as a bar coupling sleeve apparatus that comprises: a rigid contiguity 1 defining a longitudinal axis 6 and two fluidically non-communicative chambers 10 , each having an opening 9 for non-contact reception of an end portion 2 of bar of a design size; a fluid impervious barrier 8 established as part of the contiguity to define an end of each of the two fluidically non-communicative chambers; and deformations 5 established on interior walls 22 that at least partially define the chambers (perhaps it is also defined by walls of a fluid impervious barrier), wherein the interior walls and the deformations are sized so that the end portions of the bar of design size may be established within the chambers without contacting the deformations. A bar of design size is the bar for which a coupling apparatus is intended; in certain embodiments, the interior surface of such apparatus may allow for a clearance of from 1 mm to 10 mm (as one exemplary, but preferred, range) between the bar and the deformations. Of course, merely because a bar may be established within the chambers without contacting the deformations does not mean that, during field insertion of a bar end into a chamber of the apparatus, there will definitely not be contact; it merely means that such absence of contact is possible, and that fluidic clearance between the bar and the inner walls exists.
At least one embodiment of the inventive technology may be described as a bar coupling sleeve apparatus that comprises: a rigid contiguity 1 defining a longitudinal axis 6 , and having two ends 7 and openings 9 at each of the ends for reception of bar end portions; at least one fluid outlet port 4 , each enabling fluidic communication between an environment 20 external of the contiguity and one of two chambers 10 , each of which is at least partially defined by interior walls 22 of the contiguity; and deformations 5 established on the interior walls 22 , wherein the each fluid outlet port 4 is established substantially at a closed end (e.g., a barrier proximal end 21 ) of a different one of the chambers. It is of note that the apparatus, in particular embodiments, has a total of two chambers; such chambers may be fluidically non-communicative. The apparatus may further comprise a fluid impervious barrier 8 established as part of the contiguity to define an end of each of the two fluidically non-communicative chambers. It is also of note that, particularly in the two chamber embodiments, the at least one fluid outlet port may comprise at least two fluid outlet ports, each established substantially at a longitudinal midpoint of the rigid contiguity and each enabling fluidic communication between an environment external of the contiguity and a chamber at least partially defined by interior walls of the contiguity. It is of note that the term “substantially at a longitudinal midpoint of the rigid contiguity” includes up to a ¼ length portion centered at the midpoint.
At least one embodiment of the inventive technology may be described as a bar coupling sleeve apparatus that comprises: a rigid contiguity 1 defining a longitudinal axis 6 and having two ends 7 and openings 9 at both the ends for reception of bar end portions 2 ; and a fluid impervious barrier 8 established as part of the contiguity to define an end of each of two fluidically non-communicative chambers 10 within the contiguity, each of the chambers sized to accommodate a different one of the bar end portions. As in other embodiments, each of the chambers is sized to also accommodate a curable wet fluid (e.g., adhesive such as epoxy). The apparatus may further comprise two fluid outlet ports 4 , each associated with a different one of the chambers, and each enabling fluidic communication between its associated chamber and an environment external of the contiguity. Each of such two fluid outlet ports may enable fluidic communication between an environment external of the contiguity and a barrier proximal end portion of its associated chamber.
At least one embodiment of the inventive technology, more particularly focusing on the single bar retention apparatus, may be described as a bar end portion retainer apparatus that comprises: a rigid contiguity 11 defining a chamber 30 that has an opening 39 at a first end of the contiguity for reception of a bar end portion 2 ; a flange 16 established at a second end 34 of the rigid contiguity; and a fluid outlet port 14 enabling fluidic communication between the chamber 30 and an environment 20 external of the contiguity. In particular embodiments, the fluid outlet port is established proximal a terminal end 35 of the chamber 30 .
At least one embodiment of the inventive technology, more particularly focusing on the single bar retention apparatus, may be described as a bar end portion retainer apparatus that comprises: a rigid contiguity 11 defining a chamber 30 that has an opening 39 at a first end 40 of the contiguity for reception of a bar end portion 22 ; a flange 16 established at a second end 34 of the rigid contiguity; and deformations 15 established on interior walls 22 that at least partially define the chamber. The apparatus may further comprise a fluid outlet port 14 enabling fluidic communication between the chamber and an environment external of the contiguity 20 ; such fluid outlet port may be established proximal a terminal end of the chamber 35 . As with other embodiments, interior walls and the deformations may be sized so that a bar end portion of design size may be established within the chambers without contacting the deformations.
Of course, in any of the embodiments disclosed herein deformations may be established on interior walls 22 that at least partially define the chambers. Interior walls and the deformations are typically (but not necessarily always) sized so that the end portions of the bar of design size may be established within the chambers without contacting the deformations. A cross-section of the deformations in a plane that is parallel to the longitudinal axis (see FIGS. 6A and 6B ) may show a pattern having at least one section that defines a normal vector 50 that (a) has a component that is opposite to a bar withdrawal direction 51 ; and that (b) is at least 20 degrees (see angle 53 ) relative to a plane 54 that is orthogonal to the longitudinal axis. Such at least one section (that defines a normal vector with a component having limitations (a) and (b)) may be either curved (see, e.g., FIG. 6A ) or linear (see, e.g., FIG. 6B ). The at least one section may define at least one valley 55 , and the at least one section may be repeated. It is of note that even if the entire vector is in a certain direction, that it is still said that such vector has a component in that certain direction. Deformations can be made in a number of known ways, including but not limited to mechanical stress induced deformations, material addition (material addition is considered a type of deformation). Further, deformations can be of a myriad of shapes; shown in the figures are only a few examples. It is also of note that even a chamber having a substantially circular cross-section (whether with deformations or without) is viewed as having walls (plural).
In certain preferred embodiments, insertion of adhesive 3 (e.g., epoxy) into the chambers, and subsequent insertion of the bar end portions into the chamber, results in a design strength coupling after curing. In preferred embodiments, the adhesive is insertable into the chambers without pressure (application of a caulking gun is not considered a pressurized insertion, as the adhesive, after exiting the gun and while being deposited into the chamber, is not under pressure). It is of note that, in preferred embodiments, design strength is achievable without heat application or welding.
In certain embodiments having fluid outlet ports, the apparatus may be the to be configured such that when adhesive (e.g., epoxy) is inserted into the chambers and then a different one of the bar end portions is thereafter inserted into the adhesive containing chambers, fluid flows through the fluid outlet ports 4 , 14 . Indeed, the inventive apparatus may be described as including adhesive established in the chamber(s).
Of course, as alluded to throughout this description, a primary, but not exclusive, application of the various inventive technologies is rebar coupling and rebar retention. As such, the bar end portion(s) comprise rebar end portions. It is also of note that in those embodiments with a barrier (e.g., a fluid impervious barrier 8 ), such barrier may be an integral part of the contiguity (e.g., instead of being screwed or snapped into place, it is, for example, molded concurrently with the molding of the entire contiguity). The contiguity itself may be made from any of a number of materials, a metal such as steel being preferred, but certainly not the only option.
At least one embodiment of the inventive method technology may be described as a bar retention method that comprises the steps of: pressure-free packing adhesive 3 in each bar accommodative chamber 10 , 30 of a rigid contiguity; then manually establishing a bar end portion 2 in each the chamber 30 while expelling fluid through a fluid outlet port 4 , 14 ; and then curing, without heat application, the adhesive to achieve a design strength. It is of note that design strength, as used herein, may be governed by applicable code. Further, the term “pressure-free packing adhesive” merely implies placement of adhesive into the chamber without the need to overcome a pressure inside the chamber.
In those method embodiments where the rigid contiguity defines only one bar accommodative chamber, the step of pressure-free packing adhesive in each bar accommodative chamber of a rigid contiguity may comprise the step of pressure-free packing adhesive in the only one bar accommodative chamber of the rigid contiguity (see FIG. 5B , e.g.). As in other single chamber embodiments, the rigid contiguity may comprise a flange.
In those method embodiments where the rigid contiguity defines only two bar accommodative chambers, the step of pressure-free packing adhesive in each bar accommodative chamber of a rigid contiguity may comprise the step of pressure-free packing adhesive in the only two bar accommodative chambers of the rigid contiguity (see FIG. 5A , e.g.). Of course, as in other two chamber embodiments, the rigid contiguity may be described as a sleeve. Regardless of the number of chambers, the step of manually expelling fluid may comprise the step of manually expelling adhesive and/or air (e.g., through fluid outlet port(s)).
At least one embodiment of the inventive method technology may be described as a bar retention method that comprises the steps of: pressure-free packing adhesive 3 in each bar accommodative chamber 10 , 30 of a rigid contiguity 1 , 11 ; manually establishing a bar end portion 2 in each the chamber; and curing, without heat application, the adhesive to achieve a design strength. In embodiments where the rigid contiguity defines only one bar accommodative chamber, the rigid contiguity may comprise a flange 16 ; in embodiments where the rigid contiguity defines only two bar accommodative chambers, the rigid contiguity may be a sleeve. Regardless of the number of chambers, the step of expelling fluid (air and/or adhesive) through a fluid outlet port may be performed while performing the step of manually establishing. In certain embodiments, the step of manually establishing is performed after the step of pressure-free packing adhesive.
In any of the method embodiments, it is preferred that the method does not comprise the step of welding or applying heat. Also, in preferred embodiments, whether method or apparatus, end caps (that cap the open end of the chamber(s)), whether integral to the contiguity or not, are not used or needed. Further, in certain embodiments, the step of manually establishing can be performed without contacting walls 22 of each bar accommodative chamber, and each bar accommodative chamber is at least partially defined by interior walls with deformations. Of course, such deformations may be oriented as described elsewhere in this application.
It is of note that in any of the embodiments, specialized equipment (e.g., welder, pressurized adhesive applicators) may not be required (a caulking gun is not considered specialized equipment). Further, preferred embodiments do not require any screwing of any parts, as threads are preferably absent from preferred embodiments. Additionally, it should be clear that the sleeve apparatus may be used to couple a bars of different diameters. In such case, the internal diameter of the chambers may be different (although different, but closely sized rebar might not require such a difference in diameter).
As can be easily understood from the foregoing, the basic concepts of the present invention may be embodied in a variety of ways. It involves both coupling techniques as well as devices to accomplish the appropriate coupling. In this application, the coupling techniques are disclosed as part of the results shown to be achieved by the various devices described and as steps which are inherent to utilization. They are simply the natural result of utilizing the devices as intended and described. In addition, while some devices are disclosed, it should be understood that these not only accomplish certain methods but also can be varied in a number of ways. Importantly, as to all of the foregoing, all of these facets should be understood to be encompassed by this disclosure.
The discussion included in this application is intended to serve as a basic description. The reader should be aware that the specific discussion may not explicitly describe all embodiments possible; many alternatives are implicit. It also may not fully explain the generic nature of the invention and may not explicitly show how each feature or element can actually be representative of a broader function or of a great variety of alternative or equivalent elements. Again, these are implicitly included in this disclosure. Where the invention is described in device-oriented terminology, each element of the device implicitly performs a function. Apparatus claims may not only be included for the device described, but also method or process claims may be included to address the functions the invention and each element performs. Neither the description nor the terminology is intended to limit the scope of the claims that will be included in any subsequent patent application.
It should also be understood that a variety of changes may be made without departing from the essence of the invention. Such changes are also implicitly included in the description. They still fall within the scope of this invention. A broad disclosure encompassing both the explicit embodiment(s) shown, the great variety of implicit alternative embodiments, and the broad methods or processes and the like are encompassed by this disclosure and may be relied upon when drafting the claims for any subsequent patent application. It should be understood that such language changes and broader or more detailed claiming may be accomplished at a later date (such as by any required deadline) or in the event the applicant subsequently seeks a patent filing based on this filing. With this understanding, the reader should be aware that this disclosure is to be understood to support any subsequently filed patent application that may seek examination of as broad a base of claims as deemed within the applicant's right and may be designed to yield a patent covering numerous aspects of the invention both independently and as an overall system.
Further, each of the various elements of the invention and claims may also be achieved in a variety of manners. Additionally, when used or implied, an element is to be understood as encompassing individual as well as plural structures that may or may not be physically connected. This disclosure should be understood to encompass each such variation, be it a variation of an embodiment of any apparatus embodiment, a method or process embodiment, or even merely a variation of any element of these. Particularly, it should be understood that as the disclosure relates to elements of the invention, the words for each element may be expressed by equivalent apparatus terms or method terms—even if only the function or result is the same. Such equivalent, broader, or even more generic terms should be considered to be encompassed in the description of each element or action. Such terms can be substituted where desired to make explicit the implicitly broad coverage to which this invention is entitled. As but one example, it should be understood that all actions may be expressed as a means for taking that action or as an element which causes that action. Similarly, each physical element disclosed should be understood to encompass a disclosure of the action which that physical element facilitates. Regarding this last aspect, as but one example, the disclosure of a “coupler” should be understood to encompass disclosure of the act of “coupling”—whether explicitly discussed or not—and, conversely, were there effectively disclosure of the act of “coupling”, such a disclosure should be understood to encompass disclosure of a “coupling” and even a “means for coupling” Such changes and alternative terms are to be understood to be explicitly included in the description.
Any acts of law, statutes, regulations, or rules mentioned in this application for patent; or patents, publications, or other references mentioned in this application for patent are hereby incorporated by reference. Any priority case(s) claimed by this application is hereby appended and hereby incorporated by reference. In addition, as to each term used it should be understood that unless its utilization in this application is inconsistent with a broadly supporting interpretation, common dictionary definitions should be understood as incorporated for each term and all definitions, alternative terms, and synonyms such as contained in the Random House Webster's Unabridged Dictionary, second edition are hereby incorporated by reference. Finally, all references listed in the list of References To Be Incorporated By Reference In Accordance With The Patent Application or other information statement filed with the application are hereby appended and hereby incorporated by reference, however, as to each of the above, to the extent that such information or statements incorporated by reference might be considered inconsistent with the patenting of this/these invention(s) such statements are expressly not to be considered as made by the applicant(s).
Thus, the applicant(s) should be understood to have support to claim and make a statement of invention to at least: i) each of the coupler devices as herein disclosed and described, ii) the related methods disclosed and described, iii) similar, equivalent, and even implicit variations of each of these devices and methods, iv) those alternative designs which accomplish each of the functions shown as are disclosed and described, v) those alternative designs and methods which accomplish each of the functions shown as are implicit to accomplish that which is disclosed and described, vi) each feature, component, and step shown as separate and independent inventions, vii) the applications enhanced by the various systems or components disclosed, viii) the resulting products produced by such systems or components, ix) each system, method, and element shown or described as now applied to any specific field or devices mentioned, x) methods and apparatuses substantially as described hereinbefore and with reference to any of the accompanying examples, xi) the various combinations and permutations of each of the elements disclosed, xii) each potentially dependent claim or concept as a dependency on each and every one of the independent claims or concepts presented, and xiii) all inventions described herein.
With regard to claims whether now or later presented for examination, it should be understood that for practical reasons and so as to avoid great expansion of the examination burden, the applicant may at any time present only initial claims or perhaps only initial claims with only initial dependencies. The office and any third persons interested in potential scope of this or subsequent applications should understand that broader claims may be presented at a later date in this case, in a case claiming the benefit of this case, or in any continuation in spite of any preliminary amendments, other amendments, claim language, or arguments presented, thus throughout the pendency of any case there is no intention to disclaim or surrender any potential subject matter. It should be understood that if or when broader claims are presented, such may require that any relevant prior art that may have been considered at any prior time may need to be re-visited since it is possible that to the extent any amendments, claim language, or arguments presented in this or any subsequent application are considered as made to avoid such prior art, such reasons may be eliminated by later presented claims or the like. Both the examiner and any person otherwise interested in existing or later potential coverage, or considering if there has at any time been any possibility of an indication of disclaimer or surrender of potential coverage, should be aware that no such surrender or disclaimer is ever intended or ever exists in this or any subsequent application. Limitations such as arose in Hakim v. Cannon Avent Group, PLC, 479 F.3d 1313 (Fed. Cir 2007), or the like are expressly not intended in this or any subsequent related matter. In addition, support should be understood to exist to the degree required under new matter laws—including but not limited to European Patent Convention Article 123(2) and United States Patent Law 35 USC 132 or other such laws—to permit the addition of any of the various dependencies or other elements presented under one independent claim or concept as dependencies or elements under any other independent claim or concept. In drafting any claims at any time whether in this application or in any subsequent application, it should also be understood that the applicant has intended to capture as full and broad a scope of coverage as legally available. To the extent that insubstantial substitutes are made, to the extent that the applicant did not in fact draft any claim so as to literally encompass any particular embodiment, and to the extent otherwise applicable, the applicant should not be understood to have in any way intended to or actually relinquished such coverage as the applicant simply may not have been able to anticipate all eventualities; one skilled in the art, should not be reasonably expected to have drafted a claim that would have literally encompassed such alternative embodiments.
Further, if or when used, the use of the transitional phrase “comprising” is used to maintain the “open-end” claims herein, according to traditional claim interpretation. Thus, unless the context requires otherwise, it should be understood that the term “comprise” or variations such as “comprises” or “comprising”, are intended to imply the inclusion of a stated element or step or group of elements or steps but not the exclusion of any other element or step or group of elements or steps. Such terms should be interpreted in their most expansive form so as to afford the applicant the broadest coverage legally permissible.
Finally, any claims set forth at any time are hereby incorporated by reference as part of this description of the invention, and the applicant expressly reserves the right to use all of or a portion of such incorporated content of such claims as additional description to support any of or all of the claims or any element or component thereof, and the applicant further expressly reserves the right to move any portion of or all of the incorporated content of such claims or any element or component thereof from the description into the claims or vice-versa as necessary to define the matter for which protection is sought by this application or by any subsequent continuation, division, or continuation-in-part application thereof, or to obtain any benefit of, reduction in fees pursuant to, or to comply with the patent laws, rules, or regulations of any country or treaty, and such content incorporated by reference shall survive during the entire pendency of this application including any subsequent continuation, division, or continuation-in-part application thereof or any reissue or extension thereon.
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Particular embodiments of the inventive technology relate to a device for connecting the ends of two concrete reinforcing bars in which a metal sleeve has chambers at each end to accommodate the end of one reinforcing bar. Forces may be transferred from one bar to the other through, the use of, inter alia, an adhesive established within the space between the outside of the reinforcing bars and the deformed inner surface of the sleeve. The chambers are, preferably, separated by a fluid impervious barrier. One port associated with each chamber may be established to allow fluid such as air to escape, preventing air voids in the adhesive. Another configuration of the inventive device would be intended for the retention (under load, of course) of only one reinforcing bar, with an enlarged flange for anchoring the end of one reinforcing bar, perhaps at and outer surface of, e.g., a concrete slab.
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[0001] This application is a utility conversion and claims priority to Provisional Application Ser. 61/726,041 filed Nov. 14, 2012, the content of which is incorporated by reference.
BACKGROUND
[0002] This invention relates to augmenting traditional multiview stereo (MVS) reconstruction methods with semantic information such as semantic priors.
[0003] Recent years have seen rapid strides in dense 3D shape recovery, with multiview stereo (MVS) systems capable of reconstructing entire monuments. Despite this progress, MVS has remained largely applicable only in favorable imaging conditions. Lack of texture leads to extended troughs in photoconsistency-based cost functions, while specularities violate inherent Lambertian assumptions. Diffuse photoconsistency is not a reliable metric with wide baselines in scenarios with few images, leading to sparse, noisy MVS outputs. Under these circumstances, MVS reconstructions often display holes or artifacts.
[0004] On the other hand, there have been developments in two seemingly disjoint areas of computer vision. With the advent of cheap commerical scanners and depth sensors, it is now possible to easily acquire 3D shapes. Concurrently, the performance of modern object detection algorithms has rapidly improved to allow inference of reliable bounding boxes in the presence of clutter, especially when information is shared across multiple views.
SUMMARY
[0005] In one aspect, a method to reconstruct 3D model of an object includes receiving with a processor a set of training data including images of the object from various viewpoints; learning a prior comprised of a mean shape describing a commonality of shapes across a category and a set of weighted anchor points encoding similarities between instances in appearance and spatial consistency; matching anchor points across instances to enable learning a mean shape for the category; and modeling the shape of an object instance as a warped version of a category mean, along with instance-specific details.
[0006] In another aspect, given training data comprised of 3D scans and images of objects from various viewpoints, we learn a prior comprised of a mean shape and a set of weighted anchor points. The former captures the commonality of shapes across the category, while the latter encodes similarities between instances in the form of appearance and spatial consistency. We propose robust algorithms to match anchor points across instances that enable learning a mean shape for the category, even with large shape variations across instances. We model the shape of an object instance as a warped version of the category mean, along with instance-specific details. Given multiple images of an unseen instance, we collate information from 2D object detectors to align the structure from motion point cloud with the mean shape, which is subsequently warped and refined to approach the actual shape
[0007] Advantages of the preferred embodiments may include one or more of the following. The system can perform a dense reconstruction without the drawbacks of traditional multiview stereo by incorporating semantic information in the form of learned category-level shape priors and object detection. The system can perform dense reconstruction for textured surface without requiring many views. Dense reconstruction can be done with lower imaging cost (only few views required). Reconstruction can be done even for traditionally difficult surfaces, such as those without texture.
[0008] Extensive experiments demonstrate that our model is general enough to learn semantic priors for different object categories, yet powerful enough to reconstruct individual shapes with large variations. Qualitative and quantitative evaluations show that our framework can produce more accurate reconstructions than alternative state-of-the-art multiview stereo systems.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 shows an exemplary system to perform Dense Object Reconstruction with Semantic Priors.
[0010] FIG. 2 shows an exemplary process for determining semantic similarity between objects (anchor points).
[0011] FIG. 3 shows an exemplary process to learn anchor points across instances with large shape variations.
[0012] FIG. 4 shows an exemplary process to combine different shapes into a single mean shape using anchor points.
[0013] FIG. 5 shows an exemplary process to use object detection to secure aligned ment between learned shape and test reconstruction point cloud.
[0014] FIG. 6 shows an exemplary process to robustly match anchor points between shape prior and test reconstruction.
[0015] FIG. 7 shows an exemplary process to warp aligned prior shape to reconstruct SFM point cloud.
[0016] FIG. 8 shows an exemplary computer that performs the processes of FIGS. 1-7 .
DESCRIPTION
[0017] FIG. 1 shows an exemplary system to perform Dense Object Reconstruction with Semantic Priors. The system provides a framework for dense 3D reconstruction that overcomes the drawbacks of traditional MVS by leveraging semantic information in the form of object detection and shape priors learned from a database of training images and 3D shapes. Our priors are general—they are category-level and learned from training data. While object instances within a category might have very different shapes and appearances, they share certain similarities at a semantic level. For example, both sedans and sports cars have bonnets and wheels. We model semantic similarity as a shape prior, which consists of a set of automatically learned anchor points across several instances, along with a learned mean shape that captures the shared commonality of the entire category. Our experiments demonstrate that this novel representation can successfully achieve the balance between capturing semantic similarities and shape variation across instances.
[0000] Our Model: Shape=Prior+Unique Details S i =T ( S*,θ i )+Δ i
[0000] Transformation T is a weighted thin plate spline ( k+αλW −1 )β+α= x′Φ T β=0,
[0018] Unique details d obtained by minimizing
[0000]
?
?
(
d
k
i
-
(
p
k
i
-
p
k
i
)
)
2
+
μ
?
?
(
d
k
i
-
?
)
2
?
indicates text missing or illegible when filed
[0019] The process of FIG. 1 has a learning phase 200 and a reconstruction phase 300 . In the learning phase, the anchor points encode attributes such as frequency, appearance and location similarity of features across instances. The associated weights aid in discarding spurious texture matches, while determining a weighted regularization for both mean shape learning and reconstruction. Based on matched anchor points, the shape prior for a category is determined by a series of weighted thin-plate spline (TPS) warps over the scans of training objects.
[0020] Our reconstruction phase starts with a point cloud obtained by applying a structure-from-motion (SFM) or MVS system to images of an unseen instance (with a shape different from training objects). Bounding boxes from object detection in individual images are collated using the SFM camera poses and used to localize and orient the object in the point cloud. This guides the process of matching anchor points shown by green stars in right panel between the learned prior and the test object's SFM point cloud, followed by a warping of the prior shape in order to closely resemble the true shape. Finer details not captured by the shape prior may be recovered by a refinement step, using guidance from SFM or MVS output. The refinement combines confidence scores from anchor points and photoconsistency in order to produce a regularized, high quality output shape. Not only are our reconstructions visually pleasant, they are also quantitatively closer to the ground truth than other baselines.
[0021] FIGS. 2-6 show in more details the implementation of FIG. 1 . FIG. 2 shows an exemplary process for determining semantic similarity between objects (anchor points). FIG. 3 shows an exemplary process to learn anchor points across instances with large shape variations. FIG. 4 shows an exemplary process to combine different shapes into a single mean shape using anchor points. FIG. 5 shows an exemplary process to use object detection to secure aligned ment between learned shape and test reconstruction point cloud. FIG. 6 shows an exemplary process to robustly match anchor points between shape prior and test reconstruction.
[0022] We assume that for each object category, there exists a prior that consists of a 3D mean shape S* that captures the commonality of shapes across all instances and a set of anchor points A that captures similarities between subsets of instances. The shape of any particular object S i is a transformation of S*, plus specific details Δ i not shared by other instances:
[0000] S i =T ({ S*,A}, θ i )+Δ i , (1)
[0000] where T is a warping (transformation) function and θ i is the warping parameter that is unique to each object instance. In the following, we briefly explain the various aspects of our model.
[0023] One key to reconstructing an object instance is to estimate the warping parameters θ i . We leverage on certain reliable features associated with the shape prior, which we call anchor points. Anchor points form the backbone of our framework, since they are representative of object shape and the relative importance of different object structures. Anchor points with high weights, ω, are considered stable in terms of location and appearance, and thus, more representative of object shape across instances. They guide the learning of the mean shape for a category, as well as the deformation processes during actual 3D reconstruction. In Section 4.1, we detail the mechanism of learning anchor points from training data.
[0024] Warping function is discussed next. We assume that the functional form of T is known. In particular, prior work on shape matching has demonstrated inspiring results using regularized thin-plate spline (TPS) transformations to capture deformations. Let {x i } and {x′ i }, i=1, . . . , n, be two sets of anchor points for object instances O and O′. The TPS mapping T is given by
[0000]
T
(
x
,
{
α
,
β
}
)
=
∑
j
=
0
3
α
j
φ
j
(
x
)
+
∑
i
=
1
n
β
i
U
(
x
,
x
i
)
(
2
)
[0000] where φ 0 (x)=1, φ j (x)=x j and U(x, x i )=∥x−x i ∥. Note that our TPS representation is in 3D, instead of the more common 2D representation in traditional shape matching. The solution for the parameters θ={α, β} in a regularized framework is given by the system of equations:
[0000] ( K+nλI )β+Φα= x′, Φ T β=0 (3)
[0000] where K ij =U(x i , x j ), Φ ij =φ j (x i ) and λ, is a regularization parameter. Regularized TPS yields a solution that interpolates between two point sets and is sufficiently smooth. However, greater control is required for 3D reconstruction applications, since the extent of deformations must be determined by the local level of detail. Semantic information of this nature is determined automatically in our framework by the anchor point learning mechanism. To incorporate semantic information from anchor points, in the form of a weight matrix W=diag(ω 1 , . . . , ω n ), we use an extension of TPS:
[0000] ( K+nλW −1 )β+Φα=x′, Φ T β=0, (4)
[0000] which is again solvable analytically like regularized TPS.
[0025] Details specific to each object that are not captured in the shape prior are recovered by a refinement step. This refinement is used in both mean shape learning and during reconstruction of a particular test object.
[0026] To refine a shape S i (a mesh) towards shape S j , we compute displacements for vertices in S i . For a vertex p k i in S i , we estimate the surface normal n k i by a local tangent space computation. The vertex p k i is matched to p k j in S j if Pp k j −p k i P<τ 1 and |(p k j −p k i ) T n k i |<1−τ 2 , where τ 1 , τ 2 are predefined thresholds. Let P i be the set of vertices in S i that can be matched as above to the set P j in S i and N k i be the set of 1-nearest neighbors of p k i in P i . Then, the set of displacements, Δ i ={d k i }, for 1≦k≦|P i |, are computed by minimizing:
[0000]
∑
p
k
i
∈
P
i
ɛ
k
i
(
d
k
i
-
(
p
k
j
-
p
k
i
)
)
2
+
μ
∑
p
k
i
∈
S
i
∑
p
l
i
∈
N
k
i
(
d
k
i
-
d
l
i
)
2
(
5
)
[0000] where ε k i is a weight factor. The above cost function encourages the refined shape to lie closer to S j , while minimizing the local distortion induced by such displacement. The parameter μ is empirically determined for the training set. Note that (5) represents an extremely sparse linear system that can be solved efficiently. The vertices of the refined shape are obtained as p k i +d k i and it inherits the connectivity of S i .
[0027] Learning Reconstruction Priors is discussed next. For each object category, we use a set of object instances {O n } to learn a mean shape S* and a set of anchor points A. For each object instance O i in this training set, we capture a set of images I i and use a 3D scanner to obtain a detailed 3D shape S scan i . Given I i , we use a standard SFM pipeline to reconstruct a point cloud S sfm i ={p i j }, where p i j is a 3D point. We manually label a small number of SFM points, M i ={p 1 i ,p 2 i , . . . , p m i }. The labelled points M are used to align the scanned shapes {S scan i } and their reconstructed point clouds {S sfm i } in our training dataset. They also serve as the initialization for the anchor point learning, as described in the following.
[0028] An anchor point, A={Γ, χ, ω}, consists of a feature vector Γ that describes appearance, the 3D location χ with respect to the mean shape and a scalar weight ω. Γ is the aggregation of HOG features in all images where A is visible and of every object where A exists. For an anchor point A, if V are the indices of objects across which the corresponding SFM points are matched and Ω i are the indices of images of O i where A is visible, the corresponding feature vector is:
[0000] Γ={{ f k i i } k i εΩ i } iεV . (6)
[0000] where f k i i is the HOG feature of the image point associated with A in image I k i i . Let p j i be the locations of the corresponding 3D points, normalized with respect to object centroid and scale. Then, the location for the anchor point is
[0000]
χ
j
=
1
V
∑
i
∈
V
p
j
i
.
(
7
)
[0000] The weight ω reflects “importance” of an anchor point. We consider an anchor point important if it appears across many instances, with low position and appearance variance. That is,
[0000] ω= w x w α w f (8)
[0000] where
[0000]
w
x
=
exp
(
-
∑
i
≠
k
P
p
i
-
p
k
P
σ
x
N
2
)
,
w
a
=
exp
(
σ
a
N
2
)
[0000] and w f =log|V| encode location stability, appearance similarity and instance frequency, respectively. N 2 is the number of combinations. The coefficients σ α and σ x determined empirically from training data for each category. In the above,
[0000]
d
i
,
k
=
min
l
i
∈
Ω
i
,
l
k
∈
Ω
k
(
f
l
i
i
-
f
l
k
k
)
,
for
i
≠
k
,
(
9
)
[0000] where Ω i is the set of images of O i where the point is visible.
[0029] In contrast to applications like shape matching, the quality of dense reconstruction is greatly affected by the order and extent of deformations. Thus, the learned anchor point weights ω are crucial to the success of dense reconstruction. Note that while ASM frameworks also associate a weight with landmark points, they are computed solely based on location uncertainty. By encoding appearance similarity and instance frequency, we impart greater semantic knowledge to our reconstruction stage.
[0030] The key precursor to learning anchor points is matching 3D points across instances, which is far from trivial. Besides within-class variation, another challenge is the fact that most SFM points correspond to texture. Such points usually dominate an SFM point cloud, but do not generalize across instances since they do not correspond to the object shape, thus, may not be anchor point candidates. Moreover, the density of anchor points cannot be too low, since they guide the deformation process that computes the mean shape and fits it to the 3D point cloud. To ensure the robustness of anchor point matching and good density, an iterative process is shown below:
[0000]
Algorithm 1 Learning anchor points
Set Parameters δ f , δ p .
For objects O i , i ε [1, N], label m points to get M i .
Use M i to align S sfm i with S scan i .
∀p j i ⊂ M i , find A j = {Γ j ,χ j ,ω j } using (??), (9), (10).
Initialize A = {A j }, j = 1, ... , m.
while anchor point set A is updated do
for i = 1 : N do
Solve θ = arg min Σ k ||T(p k i ,θ) − χ k ||.
Warp SFM point cloud S Sfm i ← T(S sfm i ,θ).
end for
for all p k i ε S sfm i do
for all p l j ε S sfm j , where j ≠ i do
if d(f k i , f l j ) < δ f and ||p k i − p l j || < δ p then
Match p k i to p l j .
end if
end for
end for
Filter conflicting matches.
Identify sets of matched SFM points B h , h ε [1, H].
for h = 1 : H do
Find A h = {Γ h ,χ h ,ω h } using (??), (9), (10).
end for
Update A = A ∪ {A h }, for h = 1,... ,H.
end while
Output: denser anchor point set A.
[0031] Mean Shape Construction is discussed next. The learned anchor points are used to compute a mean shape for an object category. Recall that we have a mapping from the set of anchor points to each instance in the training set. Thus, we can warp successive shapes closer to a mean shape using the anchor points. The mean shape is constructed by combining these aligned and warped shapes of different instances. Since there are multiple shape instances, the order of combining them is a critical design issue, because improperly combining dissimilar shapes may introduce severe artifacts. To determine the order for combining shapes, we first measure the pairwise similarity between all pairs of training instances. In our experiments, we use the weighted number of commonly matched anchor points as the similarity cue. Given the pairwise similarities, we use hierarchical clustering to group the shapes. The similarity relationships can be represented as a binary tree where each leaf node is an object. We combine the warped shapes T(S scan i ) following the order of merging successive branches, to eventually obtain a single shape S*, which represents the commonality of all training instances. We use S* as the mean shape. The mean shape learning procedure is shown for a subset of the car dataset in FIG. 6 . Note that S* is computed by using the warped training examples, where the warping maps the 3D locations of learned anchor points. Thus, the prior shape is always aligned with the anchor points.
[0032] In the above, the warp T(S scan i )→S scan j , with i<j according to the above defined ordering, is computed as the weighted thin plate spline transformation given by (4). Two shapes aligned by anchor points are eventually combined into a single one using displacement vectors computed by minimizing (5).
[0033] The mean shape computation proceeds by systematic combination of training instances, based on a binary tree traversal. The leaf nodes of the tree are the individual training instances, with assignments based on a pairwise shape similarity computation followed by hierarchical clustering. Note that unique details are lost, while features representative of the entire class are preserved.
[0034] Semantic Reconstruction with Shape Priors is discussed next. Given a number of images of an object O, we can reconstruct its 3D shape by warping the learned prior shape S* based on the estimated θ and by recovering Δ in (1) subsequently. The reconstruction consists of three steps: matching anchor points, warping by anchor points, and refinement. Accurately recovering warp parameters θ requires accurate matches between anchor points in S* and SFM points in S sfm . This is facilitated by an initial coarse alignment between S* and S sfm .
[0035] Multiple images are used to significantly improve detection accuracy in both image and 3D space. In image I j , the detector returns the confidence value p i (u,s,π) of a detection hypothesis which appears in image location u, with scale (height and width) s and pose π. Given the estimated camera poses, a hypothesized 3D object O can be projected to each image I j at location u j , scale s j and pose π j . Thereby, the object O in 3D space may be estimated as
[0000]
O
=
arg
max
O
∑
p
j
(
u
j
,
s
j
,
π
j
)
.
(
10
)
[0000] This allows approximate estimation of the centroid, 3D pose and scale of an object. Since we also know those for the shape prior, we can use a rigid transformation to coarsely align the prior shape and its anchor points to fit the SFM point cloud of the object.
[0036] Reconstruction is discussed next. Given a set of images I of an object with unknown shape S, we use standard SFM to recover the 3D point cloud S sfm . Our goal is to use the mean shape S* to produce a dense reconstruction that closely resembles S.
[0037] Next is the Matching Anchor Points. Since the initial alignment uses the object's location, pose and scale, anchor points are likely to be aligned to 3D locations in the vicinity of their true matches. Thus, the burden of identifying the point in S sfm that corresponds to an anchor point in S* is reduced to a local search. We use HOG features to match anchor points to SFM points.
[0000] Algorithm 2 Matching anchor points Set parameters δ 1 δ 2 η. for k = 1 : K (total number of iterations) do Initialize match set B k = { }. for all A i = {Γ i ,χ i ,ω i } ε {A} do Define P = {p k ε S sfm : ||p k − χ j || < δ 1 }. Find p j ε S sfm s.t. p j = arg minp d i,j (Eq. 14) If d(f j , f i ) < δ 2 , match (A i , p j ), B k = B k ∪ {p j }. Record 3D distance r i = ||χ i − p j ||. end for Solve θ i k = arg min||T(A,θ) − B k ||. for all A i ε A do if ||T(χi,θ i k ) − b i || > r i then Discard match (A i ,b i ), B k = B k \{b i }. end if end for Solve θ k = arg min||T(A,θ) − B k ||. ∀A i ε A, χ i ← T(χi). δ 1 ← ηδ 1 . end for Output: the set of matches B K .
Warping Based on Anchor Points is detailed next. Assume S* is the shape prior after the initial alignment of Section 5.1. We use the above matches between anchor points in S* and SFM points in S sfm to estimate parameters θ for the weighted TPS warping (4) and obtain S′=T(S*,θ) that further approaches the actual shape. Notice that, this warping not only reduces the alignment error from the initial detection-based alignment, it also deforms the prior to fit the actual shape of the object.
[0038] The final step in the reconstruction process is to recover the unique details of the object. These unique details cannot be learned a priori, so they may not be captured by the warped shape S′. We use the output of an MVS algorithm, S mvs , to supply these details. While MVS may have several missing regions and outliers for the object we consider, it may reconstruct accurate oriented patches in textured or Lambertian regions where diffuse photoconsistency is a reliable metric. Using the refinement process governed by (5), we move the vertices of S′ closer to S mvs . The weights ε k now incorporate the confidence in the corresponding matched MVS point, which is encoded by the normalized cross-correlation photoconsistency.
[0039] The inventors contemplate that fine-grained recognition and detection of object parts may also benefit our semantic reconstruction framework. The system can work in an MRF-based MVS framework like, since it provides the flexibility to combine our shape prior with silhouette information from object detectors.
[0040] The invention may be implemented in hardware, firmware or software, or a combination of the three. Preferably the invention is implemented in a computer program executed on a programmable computer having a processor, a data storage system, volatile and non-volatile memory and/or storage elements, at least one input device and at least one output device.
[0041] By way of example, a block diagram of a computer to support the system is discussed next. The computer preferably includes a processor, random access memory (RAM), a program memory (preferably a writable read-only memory (ROM) such as a flash ROM) and an input/output (I/O) controller coupled by a CPU bus. The computer may optionally include a hard drive controller which is coupled to a hard disk and CPU bus. Hard disk may be used for storing application programs, such as the present invention, and data. Alternatively, application programs may be stored in RAM or ROM. I/O controller is coupled by means of an I/O bus to an I/O interface. I/O interface receives and transmits data in analog or digital form over communication links such as a serial link, local area network, wireless link, and parallel link. Optionally, a display, a keyboard and a pointing device (mouse) may also be connected to I/O bus. Alternatively, separate connections (separate buses) may be used for I/O interface, display, keyboard and pointing device. Programmable processing system may be preprogrammed or it may be programmed (and reprogrammed) by downloading a program from another source (e.g., a floppy disk, CD-ROM, or another computer).
[0042] Each computer program is tangibly stored in a machine-readable storage media or device (e.g., program memory or magnetic disk) readable by a general or special purpose programmable computer, for configuring and controlling operation of a computer when the storage media or device is read by the computer to perform the procedures described herein. The inventive system may also be considered to be embodied in a computer-readable storage medium, configured with a computer program, where the storage medium so configured causes a computer to operate in a specific and predefined manner to perform the functions described herein.
[0043] The invention has been described herein in considerable detail in order to comply with the patent Statutes and to provide those skilled in the art with the information needed to apply the novel principles and to construct and use such specialized components as are required. However, it is to be understood that the invention can be carried out by specifically different equipment and devices, and that various modifications, both as to the equipment details and operating procedures, can be accomplished without departing from the scope of the invention itself.
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A method to reconstruct 3D model of an object includes receiving with a processor a set of training data including images of the object from various viewpoints; learning a prior comprised of a mean shape describing a commonality of shapes across a category and a set of weighted anchor points encoding similarities between instances in appearance and spatial consistency; matching anchor points across instances to enable learning a mean shape for the category; and modeling the shape of an object instance as a warped version of a category mean, along with instance-specific details.
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BACKGROUND OF THE INVENTION
The present invention relates to a flexible pipe for transporting, over long distances, a fluid which is under pressure and possibly at a high temperature, such as a gas, petroleum, water or other fluids. The invention relates most particularly to a pipe intended for offshore oil exploration. It relates especially first, to the flow lines, that is to say flexible pipes unwound from a barge in order to be laid generally on the bottom of the sea and connected to the subsea installations, such pipes working mainly in static flexible pipes which are unwound from a surface installations and most of which do not lie below the seabed, such pipes working essentially in dynamic mode.
The flexible pipes used offshore must be able to resist high internal pressures and/or external pressures and also withstand longitudinal bending or twisting without the risk of being ruptured.
They have various configurations depending on their precise use but in general they satisfy the constructional criteria defined in particular in the standards API 17 B and API 17 J drawn up by the American Petroleum Institute under the tile “Recommended Practice for Flexible Pipe”. Reference may also be made to documents FR 2 654 795 A, WO 938/25 063 A, FR 2 727 738 A and FR 2 744 511 A.
A flexible pipe generally comprises, from the inside outward:
an internal sealing sheath made of a plastic, generally a polymer, able to resist to a greater or lesser extent the chemical action of the fluid to be transported;
a pressure vault resistant mainly to the pressure developed by the fluid in the sealing sheath and consisting of the winding of one or more interlocked profiled metal wires (which may or may not be self-interlockable) wound in a helix with a short pitch (i.e. with a wind angle close to 90°) around the internal sheath;
at least one ply (and generally at least two crossed plies) of tensile armor layers whose lay angle measured along the longitudinal axis of the pipe is less than 55°; and
an external protective sealing sheath made of a polymer.
Such a structure is that of a pipe with a so-called smooth bore. In a pipe with a so-called rough bore, a carcass consisting of an interlocked metal strip, which serves to prevent the pipe being crushed under external pressure, is also provided inside the internal sealing sheath. However, the pressure vault also contributes to the crushing strength.
Attempts are made to reduce the weight of flexible pipes, particularly for applications at great depth, where, in order to rests being crushed, it is necessary to considerably increase the moment of inertia of the profiled wire constituting the pressure vault. The weight of the flexible pipe also plays an important role when laying it; this is because its weight must be limited so as to allow it no be laid by existing means (for example 600 tonnes for a conventional system).
The pressure vault consists of a profiled wire, usually of the Z or T type, or derivatives (teta and zeta) thereof, which is wound with a short pitch. The profiled wire is generally such that the ratio of its height to its width is less than 1, so as to prevent warping in winding the vault. In addition, it is known to dimension the pressure vault so that it helps to delay the onset of ovalization of the carcass under the increase in internal pressure (this onset resulting in the ruin of the carcass), but promotes the extension of the preferred cardioidal deformation mode: the delay in ovalization is all the greater the higher the moment of inertia I xx , of the profiled wire constituting the vault.
For applications at great depth, it is therefore desired to increase the moment of inertia of the profiled wire usually employed, in order to resist the crushing pressure; for example, it would be desirable to use a teta wire 16 mm in height. However, this would result in drawbacks, such as the increase in the weight of the pipe which may exceed the limit of the laying system, or even exceed the limits of resistance of the pipe itself being able to support its own weight when laying it; and a more complex implementation of this type of profiled wire; all these drawbacks increase the manufacturing cost of such a pipe.
The oil industry is therefore seeking an interlockable profiled wire having a high moment of inertia I xx for a low weight.
It has already been proposed, in document U.S. Pat. No. 4,549,581 A, to use interlockable U-shaped profiled wires, but the improvement made to the moment of inertia/weight ratio has not been significant. Moreover, it appears not to be easy to envision lightening the known S-, Z- or T-shaped sections by providing hollows, for manufacturing reasons.
SUMMARY OF THE INVENTION
The objective of the invention is therefore to propose a novel type of interlockable section allowing the moment of inertia/weight ratio to be very favorably increased.
The objective of the invention is achieved by providing a flexible tubular pipe comprising at least, from the inside outward, an internal sealing sheath, a cylindrical pressure vault consisting of the winding of an interlocked profiled metal wire wound in a helix with a short pitch, at least one ply of tensile armor layers wound with a long pitch, and an external protective sealing sheath made of a polymer, characterized in that the profiled wire constituting the vault has an I-shaped cross section.
I-shaped (or H-shaped) sections have already been proposed within the specific framework of flexodrilling, for example in documents FR 2 210 267 A or FR 2 229 913 A. However, these sections are used to produce the tensile armor layers, that is to say they are in the form of windings of non-interlockable wires with a long pitch, whereas the pressure vault is always produced with S- or Z-shaped interlockable profiled wires. Moreover, in this flexodrilling application, the proposed wires have a height/width ratio greater than 1 and a moment of inertia I xx /moment of inertia I yy ratio of preferably between 1.5 and 2. Such a wire would neither allow the necessary bending nor the stability during winding with a short pitch (warping phenomenon).
Also known, from document GB 1 081 339 A, is a hose formed from a short-pitch winding of a box strip having an I-shaped cross section, the flanges of the I being flexible enough to be able, by deformation, to be imbricated one with respect to another. The hose in question has nothing to do with the pipes of the invention since it does not have either a pressure vault or any tensile armor layers, and is not intended for the same application. The winding does not in itself present any difficulty because it is a strip which, even boxed, remains very flexible. Besides, the height-to-width ratio of the I formed by the strip is very low (typically less than ⅓), which allows it to be easily wound.
The present invention differs from this in that it is a true profiled wire, that is to say a wire of relatively large cross section (with a mean diameter generally greater than 10 mm), which cannot be likened to a simple strip. In addition, according to the invention, the ratio of the height to the width of the I is preferably between 0.5 and 1 and even between 0.7 and 0.8.
Advantageously, the wire forms an I with thick flanges in which recesses are formed, these being intended to at least partially house fasteners, for example the flanges of U-shaped fasteners.
These recesses may be formed on the inside of the flanges, but are preferably formed on the outside of the flanges, in order to facilitate the fastening. They may be formed toward the ends of the flanges or indeed formed at the center of the flanges.
The invention will be clearly understood with the aid of the description which follows, with reference to the appended schematic drawings showing, by way of example, embodiments of the flexible pipe according to the invention. Further advantages and features will become apparent on reading the description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic perspective view showing the successive layers of a pipe (in the present case, of the smooth-bore type) to which the invention applies.
FIG. 2 is a partial view in longitudinal section of a first embodiment of a flexible pipe according to the invention, the metal vault being formed from an I-shaped metal wire wound as a helix and fastened from above.
FIG. 3 is a partial view in longitudinal cross section of a second embodiment of a metal vault according to the invention.
FIGS. 4 to 16 show, in schematic partial cross section, five alternative forms of the I-shaped section for a profiled wire according to the invention, these being combined, where appropriate, with various fastening means.
FIG. 17 is a graph showing, for various types of profiled wire, the relationship between the moment of inertia×modulus and the weight per meter of pipe.
DESCRIPTION OF PREFERRED EMBODIMENTS
It should be noted that in some of the figures the spaces between the constituent elements have sometimes been intentionally exaggerated in order to make the drawings clearer.
As FIG. 1 shows, and in general, a pipe of the smooth-bore type comprises, from the inside outward, a polymeric internal sealing sheath 1 , a metal vault 2 consisting of the winding of at least one profiled metal wire wound in a helix with a short pitch, an armor layer 30 resistant to the axial tension in the longitudinal direction of the pipe and usually consisting of one or more pairs of crossed plies 31 , 32 of a winding with a long pitch in opposite directions, and a polymeric external sealing sheath 33 . Other layers (not shown) may be provided, depending on the type and the application of the pipe, such as, for example, an internal carcass underneath the internal sealing sheath 1 (for so-called rough-bore pipes which are the preferred type of application of the invention), a hoop reinforcement layer consisting of a winding of a rectangular wire with a short pitch, interposed between the pressure vault 2 and the first armor ply 31 , and intermediate sheaths placed between various armor plies.
FIG. 2 shows, in longitudinal cross section, an example of a pressure vault 2 according to the invention, formed from a profiled wire 10 of large cross section and therefore of large moment of inertia, but lightened since it consists of a profiled wire having a cross section in the form of an upright I (or an H on its side), which has a web 3 and flanges 4 , 5 , 6 and 7 , the web 3 being wound approximately radially over and around the internal sheath 1 in a helix with a short catch, the external flanges 4 , 5 and the internal flanges 6 , 7 of the consecutive turns facing each other and together forming an approximately confined volume 8 helically traversing the vault 2 .
The shape of the flanges may be highly varied, as may be seen below, as long as the flanges 6 , 7 on the internal side, or the flanges 4 , 5 on the external side, allow the wire to be interlocked. This is achieved either by self-interlocking by virtue of a special section given to the profiled wire, or by an attached interlocking wire which it is generally preferred to place on the outer face of the vault (so-called fastening “from above”) both for reasons of ease of manufacture and of better strength of the pipe, especially when it is used in dynamic mode (riser).
In the embodiment shown in FIG. 2, the I-shaped metal wire 10 of the pressure vault 2 of the flexible pipe is interlocked by a fastener 11 on the external face of the vault; the fastener 11 consists of a wire in the form of a flat U wound helically in recesses 14 of the external face of the vault 2 , that is to say by the outer flanges 4 and 5 of the metal wire 10 , and it joins together, at these outer flanges 4 and 5 , the consecutive turns of the helically wound metal wire 10 . The fastener 11 is advantageously placed slightly set back with respect to the volume envelope of the external face so as to prevent the armor layers from bearing on the fastener 11 , which would run the risk of inducing fatigue in dynamic use.
To give a pipe flexibility, the metal wire 10 is wound helically by leaving internal and external helical gaps on the respectively internal and external faces of the pressure vault, these caps opening onto the internal volume 8 . In order to prevent the possibility of the sheath 1 creeping between the flanges 6 and 7 of two consecutive turns, it is advantageous to provide an anti-creep device consisting of an overlay element 12 produced, in FIG. 2, by the overlap of the parts 20 , 21 of the unsymmetrical flanges 6 , 7 facing the internal sheath 1 . These parts 20 , 21 overlap longitudinally so that they allow the formation of the longitudinal gap 9 but, on the other hand, leave virtually no passage in the thickness direction of the flanges, so as to bar access between the sheath 1 and the confined volume 8 .
FIG. 3 shows in greater detail a preferred embodiment of the I-shaped profiled wire fastened from above by means of a fastener 11 similar to that in the embodiment of FIG. 2 and intended for dynamic applications. The anti-creep overlay element 12 consists here of a flat wire, for example made of PTFE-coated metal, wound helically in the inner face of the vault 2 , in the symmetrical inner flanges 6 and 7 of the metal wire 3 , by means of facing recessed parts 13 made over the length of the flanges 6 and 7 of the consecutive turns of the metal wire 3 which are the furthest inside the pipe. These recessed parts 13 are substantially in shape correspondence with said overlay element 12 so that the latter 12 can be easily housed therein, at least partially.
The wire 10 is in the form of a I with a height H and a width L, its web 3 having a thickness l. The flanges have a height a and are joined to the web by a surface 15 approximately in the form of a dihedron with a rounded peak, the dihedron making an angle α with a plane parallel to the base of the flanges, this angle being determined by the rolling conditions for and the constraints on the I (the position of the center of gravity, distribution of the stresses, weight). These surfaces 15 are joined to the web by a rounded piece whose radius of curvature is defined by the rolling options. It has been discovered according to the invention that, in order to obtain the desired weight saving for the same moment of inertia, it is preferable to have:
(1) I xx /I yy <1 (xx and yy denoting the respective horizontal and vertical axes with respect to the I);
(2) 0.5<H/L<1 and preferably, (2′), 0.7<H/L<0.8;
(3) 0.2<l/L<0.6 and preferably, (3′), 0.3<l/L<0.5;
(4) 0<α<45° and preferably, (4′), 10°<α<30°.
With regard to the interlocking, this is achieved so as to allow the adjacent interlocked wires to be separated by a clearance of between a zero minimum clearance (see the two wires on the left in FIG. 3) and a maximum clearance (see the two wires on the right in FIG. 3 ), to which clearances a minimum pitch and a maximum pitch correspond, the half-sum of which pitches is the mean pitch P m . The recesses 14 , of width C, are limited by a rim of width J and of height M and are separated by a distance F. The recesses, which are here represented by right-angled walls, may be flared; in this case, the profile of the fastener is modified accordingly. The U-shaped fasteners 11 have a thickness e and a width D and their feet 17 have a height G and a width U. The back of the fasteners 11 is set in by a small distance b with respect to the level of the I-shaped section. Preferably:
(5) G and M>0.5 mm and preferably G and M>1 mm, with G<M;
(6) C>1 mm and preferably 2 mm, with C<U+10%P m ;
(7) P m <10L/9;
(8) thickness e>1 mm, and preferably 2 mm;
(9) set-back b of about 0.1 mm;
(10) D+F<L;
(11) I−2J<10%P m .
To be more specific, the characteristic dimensions of the preferred embodiment in FIG. 3 are the following: H=22 mm; L=28.6 mm; H/L=0.77; 1=12 mm; maximum pitch=33 mm; mean pitch=30.8 mm; e=G=2 mm; D=13.3 mm; depth of the recesses 14=4.2 mm. For the same moment of inertia, it may be shown that this I-shaped cross section allows a weight saving of 25% over a conventional teta-shaped cross section. This is illustrated in FIG. 17 in which the relationship between the moment of inertia×modulus as a function of the weight per meter of the structure (for a 12″, i.e. approximately 30 cm, pipe) has been compared for various profiled wire sections, namely conventional steel and aluminum teta-shaped and steel U-shaped sections and steel I-shaped sections according to the invention. It may be seen that, apart from the aluminum teta, which is necessarily lighter, the steel I according to the invention favorably decreases he weight/moment of inertia ratio compared with the teta-shaped and even the U-shaped wire.
Although the “cactus-shaped” section in FIG. 3 represents a preferred embodiment of the invention, many other forms are possible, including some of those illustrated in FIGS. 4 to 16 .
In FIGS. 4 and 5, the I-shaped section 10 has, at its base, recesses 14 ′ intended for interlocking from the bottom by means of a U-shaped fastener 11 similar to that described in the previous embodiment. This method of interlocking from below is, in principle, reserved for use of the pipe in static mode.
FIGS. 6 to 9 illustrate possible sections for the wire 10 , the arrangements corresponding to the method of interlocking adopted not having been shown in some of these figures.
In FIG. 6, the width of the upper flanges 4 and 5 of the symmetrical section has been reduced. This section is advantageously interlocked on the inside, as shown in FIG. 13, by U-shaped fasteners 11 placed in housings 14 ″ formed on the upper part of the lower flanges 6 , 7 and an element, such as a seal, may be placed on top of the fastener 11 .
FIG. 7 shows a section similar to a basic I, the upper flanges 4 , 5 of which have been modified so as to include self-interlocking hooks 18 .
FIG. 8 shows a section 10 with unsymmetrical flanges 4 , 5 and 6 , 7 , allowing self-interlocking from above and from below, the latter solution being illustrated in FIG. 14, which shows self-interlocking hooks 18 formed in a complementary manner on the flanges 6 , 7 .
FIG. 9 shows a I-shaped section 10 with a very high moment of inertia by virtue of the large thickness of the flanges 4 to 7 , which terminate in a rim 19 . The rim 19 may serve for the interlocking, unless an interlocking method like that in FIGS. 15 or 16 (described later) is chosen.
Previously, interlocking via the flanges, either on the top side or on the bottom side, where the flanges of the U-shaped fasteners 11 are housed in recesses 14 placed entirely in the flanges of the I-shaped section, was described. This allows the fastener 11 to be completely retracted but it requires making the flanges which receive the recesses 14 sufficiently thick.
Provision may also be made for the recesses 14 for housing he fasteners to be closer to the mid-plane of the section 10 , or even at the point of forming only a single central groove housing the flanges of the two adjacent U-shaped fasteners 11 , as shown in FIG. 10 (interlocking from above) and FIG. 11 (interlocking from below). In this case, the fasteners 11 are no longer retracted.
Up until now U-shaped fasteners have been described, but it goes without saying that other fastener sections may be adopted, for example a zeta section like that illustrated in FIG. 12 which shows a zeta fastener 11 ′″, the edges of which are housed in recesses 14 ′″ provided on the respective lower and upper faces of the flanges 6 and 7 (interlocking from below).
FIG. 15 shows an embodiment of interlocking by straddling, which does not require a recess for housing the flanges of the fasteners; in this case, the fasteners 11 ′ in the form of a wide U straddle two I-shaped sections 10 , the upper fasteners being offset with respect to the lower fasteners so that the combination of the two fastener wires allows the sections 10 to be effectively held together between their flanges.
In FIG. 16, the straddling fasteners 11 ′ are similar to those in the previous figure, except that they are housed in central grooves 14 , alternatively at the top and at the bottom, of the sections 10 which are similar to those in FIGS. 10 and 11.
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A flexible tubular pipe having an internal sheath and a pressure vault around the sheath with a helically would short pitch metal wire. The metal wire has an I-shaped cross-section with a narrowed central web and greater thickness internal and external flanges. Recesses in at least one set of the flanges enable fastening elements to be installed for holding to adjacent wire windings. The ratios of widths of the flanges, height and width of the wire, moments of inertia in the width wise and radial direction are disclosed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of pending U.S. patent application Ser. No. 09/389,862, filed Sep. 2, 1999. Now U.S. Pat. No. 6,492,738.
TECHNICAL FIELD
The present invention relates to apparatus and methods of testing and assembling bumped die and bumped devices using an anisotropically conductive layer, suitable for testing, for example, flip chip die, chip scale packages, multi-chip modules, and the like.
BACKGROUND OF THE INVENTION
Bumped die and other bumped devices are widely used throughout the electronics industry. As the drive toward smaller electronics continues, the pitch (or spacing) of solder bumps on such bumped devices continues to decrease. The increasingly finer pitches of the solder bumps on bumped die and bumped devices raise concerns about the reliability of these devices. These concerns are being addressed by testing.
A die (or chip) is typically tested during the manufacturing process to ensure that the die conforms to operational specifications. Solder bumps (or balls) are then formed on bond pads of the die using a solder deposition device, such as a solder ball bumper. The solder bumps are typically formed with a height of from 25 μm to 75 μm. The bumped die are then tested by placing conductive test leads in contact with the solder bumps on the die, applying a test signal to the bumps via the test leads, and determining whether the bumped die responds with the proper output signals. If the bumped die tests successfully, it may be installed on a printed circuit board, a chip scale package, a semiconductor module, or other electronics device.
FIG. 1 is a cross-sectional view of a bumped die 10 engaged with a test carrier 20 in accordance with the prior art. In this typical arrangement, the bumped die 10 includes a substrate 12 with a plurality of bond pads 14 thereon. A solder bump 16 (or other suitable conductive material) is formed on each of the bond pads 14 . The test carrier 20 has a plurality of contact pads 22 thereon, each of the contact pads 22 being electrically coupled with a test lead 24 . For testing of the bumped die 10 , the solder bumps 16 engage the contact pads 22 of the test carrier 20 , and the appropriate test signals are applied to the bumped die 10 through some of the test leads 24 . Output signals from the bumped die 10 are monitored through other test leads 24 to determine whether the bumped die 10 is functioning to specifications. Test carrier apparatus of the type shown in FIG. 1 for testing unpackaged die are described in U.S. Pat. No. 5,519,332 to Wood et. al, incorporated herein by reference.
Testing of the bumped die 10 generally includes four levels of testing. A first or “standard probe” level includes the standard tests for gross functionality of die circuitry. A second or “speed probe” level includes testing the speed performance of the die for the fastest speed grades. A third or “bum-in die” level involves thermal cycling tests intended to drive contaminants into the active circuitry and to detect early failures. And a fourth or “known good die (KGD)” level includes testing to provide a reliability suitable for final products.
To ensure proper transmission of the test signals and output signals, the solder bumps 16 may be temporarily connected with the contact pads 22 by reflowing the bumps, thereby soldering the bumps to the contact pads. After the testing is complete, the solder bumps 16 may be reflowed to disconnect the bumps from the contact pads. Connecting and disconnecting the solder bumps 16 from the contact pads 22 , however, involve time consuming processes and may damage the solder bumps 16 or the contact pads 22 .
Another problem with soldering the solder bumps 16 to the contact pads 22 is that the coefficient of thermal expansion (CTE) of the bumped die 10 may be appreciably different from the CTE of the test carrier 20 . During bum-in die testing, the bumped die 10 and test carrier 20 are placed in a bum-in oven and subjected to temperature cycling (e.g. −55° C. to 150° C.) for a time period of from several minutes to several hours or more. Due to the different CTE of the bumped die 10 and the test carrier 20 and the rigidity of the solder connections, significant stresses may develop throughout the components. These stresses may result in delamination or other damage to the bumped die 16 or the test carrier 20 , and may degrade or damage the connection between the solder bumps 16 and the bond pads 14 .
An alternate approach to soldering is to simply compress the solder bumps 16 into engagement with the contact pads 22 . Ideally, only a small compression force is needed to engage the solder balls 16 against the contact pads 22 so that tests may be conducted. Methods and apparatus for testing die in this manner are fully described in U.S. Pat. No. 5,634,267 to Farnworth and Wood, incorporated herein by reference. The applied compression force, however, must be kept to a minimum because larger forces may damage the circuitry of the bumped die 10 or the test carrier 20 .
A problem common to both the solder reflow and the compression force methods of engagement is that the solder bumps 16 are not uniformly shaped. As shown in FIG. 1, the solder bumps 16 are usually of different heights. Using typical manufacturing methods and solders, the nominal variation between the tallest and shortest bumps (shown as a distance d on FIG. 1) is presently about 10% of the average solder ball height. Therefore, when the bumped die 10 is placed on the test carrier 20 , the shorter solder bumps may not touch the corresponding contact pads. In some cases, especially for very fine pitch solder bumps, the gaps between the shorter solder bumps and the contact pads may be too large to overcome using solder reflow (because of the small volume of solder in each bump) or by using compression force (because of possible damage to the bumped die).
The variation in solder bump height also creates uncertainty in the final assembly of electronics components that include bumped devices. As the number of bumps on the bumped device increases, the failure rate of the assembled package increases due to solder bump non-uniformity.
FIG. 2 is a partial cross-sectional view of the bumped die 10 of FIG. 1 engaged with another conventional test carrier 40 . The test carrier 40 includes a test substrate 42 having a plurality of pockets 44 disposed therein. As shown in FIG. 2, the pockets 44 have sloping sidewalls 46 , and a pair of contact blades 48 project from opposing sidewalls 46 into each pocket 44 . Conductive test leads 50 are formed on the test substrate 42 , including on the sidewalls 46 and contact blades 48 of the pockets 44 .
During testing, the solder bumps 16 at least partially engage the pockets 44 of the test carrier 40 with the sharp contact blades 48 partially penetrating the solder bumps 16 . The solder bumps 16 may also contact the sloping sidewalls 46 of the test carrier 40 . Thus, the desired electrical connection between the solder bumps 16 and the test leads 50 may be achieved despite the variation in the solder bump height.
Although the test carrier 40 having pockets 44 with contact blades 48 addresses solder bump height variation, testing solder bumps with the test carrier 40 has several disadvantages. For example, because the contact blades 48 penetrate the solder bumps 16 , the solder bumps may be cracked, chipped, or otherwise damaged by the contact blades. The solder bumps 16 may also become stuck to the contact blades 48 , requiring additional time and effort to disengage the bumped die 10 from the test carrier 40 . Furthermore, the test carrier 40 with the plurality of pockets 44 is relatively costly to fabricate and more difficult to maintain than alternative test carriers having flat contact pads.
FIG. 3 is a partial cross-sectional view of the bumped die 10 of FIG. 1 engaged with another prior art test carrier 60 . In this example, the test carrier 60 includes a test substrate 62 having a plurality of pedestals 64 formed thereon. Test leads 66 are disposed on the test substrate 62 , each test lead 66 terminating in a contact pad 68 on the top of each pedestal 64 . A plurality of projections 69 project from each contact pad 68 . Apparatus for testing semiconductor circuitry of the type shown in FIG. 3 are more fully described in U.S. Pat. No. 5,326,428 to Farnworth et. al., U.S. Pat. No. 5,419,807 to Akram and Farnworth, and U.S. Pat. No. 5,483,741 to Akram et. al., which are incorporated herein by reference.
To conduct a test of the bumped die 10 , the solder bumps 16 engage the contact pads 68 so that the sharp projections 69 at least partially penetrate the solder bumps 16 . The projections 69 may be properly sized to penetrate into the taller solder bumps, allowing the shorter solder bumps to at least contact the projections of the corresponding contact pad 68 .
One of the drawbacks of testing bumped die using the carrier 60 having projections 69 is that the projections (like the contact blades 48 described above) may damage the solder bumps 16 . Furthermore, the projections 69 are relatively expensive to manufacture, particularly when the projections must be sized to account for a nominal 10% variation in the solder bump height.
SUMMARY OF THE INVENTION
The present invention is directed toward apparatus and methods of testing and assembling bumped devices using anisotropically conductive layers. In one aspect of the invention, a semiconductor device comprises a bumped device having a plurality of conductive bumps formed thereon, a substrate having a plurality of contact pads distributed thereon and approximately aligned with the plurality of conductive bumps, and an anisotropically conductive layer disposed between and mechanically coupled to the bumped device and to the substrate. The anisotropically conductive layer electrically couples each of the conductive bumps with a corresponding one of the contact pads, providing electrical contact between the conductive bumps and the contact pads despite variation in conductive bump height, and without damaging the conductive bumps.
In another aspect, an apparatus for testing a bumped device having plurality of conductive bumps includes a substrate having a plurality of contact pads distributed thereon and substantially alignable with the plurality of conductive bumps, and an anisotropically conductive layer disposed on the first surface and engageable with the plurality of conductive bumps to electrically couple each of the conductive bumps with a corresponding one of the contact pads. Alternately, the test apparatus may also include an alignment device. In another aspect, the test apparatus may include a bumped device handler. The test apparatus provides for rapid and efficient engagement, testing, and disengagement of the bumped device.
In another aspect of the invention, a method of forming a semiconductor device includes providing a bumped device having a plurality of conductive bumps formed thereon, providing a substrate having a plurality of contact pads distributed thereon, forming an anisotropically conductive layer between the conductive bumps and the contact pads, approximately aligning the plurality of conductive bumps with the plurality of contact pads, and engaging the plurality of conductive bumps and the plurality of contact pads with the anisotropically conductive layer to electrically couple each of the conductive bumps with a corresponding one of the contact pads.
In yet another aspect of the invention, a method of testing a bumped device includes engaging a plurality of contact pads with an anisotropically conductive layer, engaging the plurality of conductive bumps with the anisotropically conductive layer substantially opposite from and in approximate alignment with the plurality of contact pads, forming a plurality of conductive paths through the anisotropically conductive layer so that each of the conductive bumps is electrically coupled to one of the contact pads, and applying test signals through at least some of the contact pads and the conductive paths to at least some of the conductive bumps. Alternately, the method further includes at least partially curing the anisotropically conductive layer. The method advantageously reduces the time, effort and expense involved in connecting and disconnecting the conductive bumps from the contact pads, reduces the potential for damage to the conductive bumps or the contact pads, and accommodates variation in the heights of the conductive bumps.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a bumped die engaged with a test carrier in accordance with the prior art.
FIG. 2 is a partial cross-sectional view of the bumped die of FIG. 1 engaged with an alternate embodiment of a test carrier in accordance with the prior art.
FIG. 3 is a partial cross-sectional view of the bumped die of FIG. 1 engaged with another embodiment of a test carrier in accordance with the prior art.
FIG. 4 is a partial cross-sectional view of the bumped die of FIG. 1 engaged with a test carrier in accordance with an embodiment of the invention.
FIG. 5 is a partial cross-sectional view of the bumped die of FIG. 1 engaged with a test carrier in accordance with an alternate embodiment of the invention.
FIG. 6 is a partial cross-sectional view of the bumped die of FIG. 1 engaged with a test carrier in accordance with another alternate embodiment of the invention.
FIG. 7 is a partial cross-sectional view of the bumped die of FIG. 1 engaged with a test carrier in accordance with yet another embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The following description is generally directed toward apparatus and methods of testing and assembling bumped die and bumped devices using anisotropically conductive layers. Many specific details of certain embodiments of the invention are set forth in the following description and in FIGS. 2-7 to provide a thorough understanding of such embodiments. One skilled in the art, however, will understand that the present invention may have additional embodiments, or that the present invention may be practiced without several of the details described in the following description.
Throughout the following discussion, apparatus and methods in accordance with the invention are described in relation to the testing and assembly of bumped die. It is understood, however, that the inventive apparatus and methods may be used to test and assemble any number of bumped devices, including chip scale packages, chip modules, or any other bumped devices. To simplify the following discussion, however, the inventive apparatus and methods are described in relation to testing and assembly of bumped die with a test carrier or a printed circuit board, allowing the reader to focus on the inventive aspects.
FIG. 4 is a partial cross-sectional view of the bumped die 10 of FIG. 1 engaged with a test carrier 100 in accordance with an embodiment of the invention. In this embodiment, the test carrier 100 includes a test substrate 102 having a plurality of contact pads 104 coupled with a plurality of test leads 106 . An anisotropically conductive layer 160 having conductive particles 162 distributed in a suspension material 164 is formed on the test substrate 102 and contact pads 104 .
The anisotropically conductive layer 160 is formed such that electrical resistance in one direction through the layer 160 differs from that measured in the other directions. Typically, electrical conductivity is provided in one direction (e.g. the “z” direction) while high resistance is provided in all other directions. The conductivity in the one direction may be pressure sensitive, requiring that the material be compressed in that direction to achieve the desired conductivity.
One type of anisotropically conductive material suitable for forming the anisotropically conductive layer 160 is known as a “z-axis anisotropic adhesive.” In the z-axis anisotropic adhesive, the conductive particles 162 are distributed to a low level such that the particles do not contact each other in the xy plane. Compression of the layer 160 in the z direction, however, causes the conductive particles 162 to contact each other in the z direction, establishing an electrically conductive path. The conductive particles 162 may be formed from any suitable electrically conductive materials, such as gold, silver, or other electrically conductive elements or compounds. Similarly, the suspension material 164 may be include, for example, a thermoset polymer, a B-stage (or “pre-preg”) polymer, a pre-B stage polymer, a thermoplastic polymer, or any monomer, polymer, or other suitable material that can support the electrically conductive particles 162 .
Z-axis anisotropic adhesives may be formed in a number of ways, including, for example, as a film or as a viscous paste that is applied (e.g. stenciled, sprayed, flowed, etc.) to the contact pads 104 . The anisotropically conductive adhesives may then be cured. Curing may be performed in a variety of ways, such as by subjecting the materials to certain environmental conditions (e.g. temperature, pressure, etc.), or by the removal of solvents or suitable curing compounds, or by irradiation/exposure to ultraviolet or ultrasonic energy, or by other suitable means.
For example, z-axis anisotropic adhesives are commercially available in both a thermoplastic variety or a thermosetting variety.
Thermoplastic anisotropic adhesives are those that are heated to soften for application to the test substrate and then cooled for curing, and include, for example, solvent-based hot-melt glue. Conversely, thermosetting anisotropic adhesives are suitable for application to the test substrate at normal ambient temperatures, and are heated for curing at temperatures from 100° C. to 300° C. for periods from several minutes to an hour or more. Suitable z-axis anisotropic adhesives include those available from A.I. Technology, Inc. of Trenton, N.J., or Sheldahl, Inc. of Northfield, Minn., or 3M of St. Paul, Minn.
As best seen in FIG. 4, the anisotropically conductive layer 160 is formed on the test substrate 102 , and the bumped die 10 is positioned adjacent to the layer 160 with the solder (or conductive) bumps 16 approximately aligned with the contact pads 104 . The bumps 16 may alternately be formed of any suitable, electrically conductive material. For bumped die 10 having solder bump pitches of at least 32 μm, conventional mechanical alignment devices may be used. For finer pitches, however, more advanced optical alignment systems may be necessary, such as the type of alignment apparatus shown and described in U.S. Pat. No. 4,899,921 to Bendat et. al., incorporated herein by reference.
In the test carrier 100 , the solder bumps 16 are compressed into the anisotropically conductive layer 160 prior to the curing of the layer 160 so that the solder bumps 16 become embedded in the layer 160 . The compression of the solder bumps 16 into the anisotropically conductive layer 160 compresses the conductive particles 162 into contact with each other and creates an electrically conductive path 166 between each of the solder bumps 16 and its corresponding contact pad 104 .
In the test carrier 100 , the solder bumps 16 become attached to the test carrier 100 during the curing of the anisotropically conductive layer 160 . For example, in one embodiment, an anisotropically conductive layer 160 having a B stage polymer as the suspension material 164 is applied to the test carrier 100 . A bumped die 10 is pressed into the layer 160 until the solder bumps 16 are “tacked” in position, and then the bumped die 10 and test carrier 100 are placed in an oven and heated to 150° C. At this temperature, the polymer is fully cross-linked, curing the layer 160 to a hardened consistency.
One or more test signals are then transmitted to the bumped die 10 through one or more of the test leads 106 , through the contact pads 104 , across the conductive paths 166 , through the solder bumps 16 , and into the bumped die 10 . Output signals from the bumped die 10 are then communicated from the solder bumps 16 back across the conductive paths 166 to the contact pads 104 and other test leads 106 , and are monitored to determine whether the bumped die 10 is functioning to the desired specifications.
After testing, the bumped die 10 may be removed from the test carrier 100 by detaching the solder bumps 16 from the anisotropically conductive layer 160 . This may be accomplished in a number of ways depending upon the properties of the anisotropically conductive layer 160 , including, for example, by heating the layer 160 until it softens, or by applying solvents to dissolve the layer, or by other suitable means. After the bumped die 10 is removed, the test carrier 100 may be used to test another bumped die 10 .
Alternately, FIG. 4 may represent a cross-sectional view of the bumped die 10 attached to any electronic component, such as a printed circuit board 100 . In that case, the bumped die 10 may be aligned with the contact pads 104 and attached with the anisotropically conductive layer 160 as described above, except that the bumped die 10 is not removed and remains secured to the printed circuit board 100 .
Although the anisotropically conductive layer 160 is shown in FIG. 4 as being a single, continuous layer covering the entire test substrate 102 , it is not necessary that only one layer be used, or that the layer be continuous. Rather, the anisotropically conductive material may be formed on a plurality of contact pads 104 of the test carrier (or printed circuit board) 100 in a variety of patterns, including, for example, in strips covering rows of contact pads, or in a checkerboard pattern covering regions of contact pads.
Furthermore, it is not necessary that the anisotropically conductive layer 160 be formed on the test carrier (or printed circuit board) 100 , but rather, the layer 160 might be formed on the solder bumps 16 of the bumped die 10 . After the layer 160 is applied to the solder bumps 16 , the test carrier 100 may be engaged with the layer to form the desired electrical connections for testing of the die.
The anisotropically conductive layer 160 advantageously improves the process of testing and assembling of bumped die 10 and other bumped devices. The process of attaching (and detaching) the bumped die 10 to the test carrier (or printed circuit board) 100 using the anisotropically conductive layer 160 may be less time consuming and more economical than the prior art process of soldering (and unsoldering) the solder bumps 16 to (and from) the contact pads 104 because the rework temperatures of the anisotropically conductive layer 160 (typically 80° C. to 150° C.) may be less than the typical reflow temperature of solder (183° C.). Thus, less time and energy may be needed to bring the temperatures of the bumped die 10 and test carrier 100 up to the temperature necessary for detachment, and the potential for damaging the solder bumps 16 or the contact pads 104 may be decreased due to the reduced rework temperatures.
Another advantage of the test carrier (or printed circuit board) 100 having the anisotropically conductive layer 160 is that a more flexible connection may be provided between the solder bumps 16 and the contact pads 22 than is obtained using solder. If the bumped die 10 and test carrier 100 are subjected to a large range of temperatures or repeatedly thermal cycling during the testing (e.g. burn-in tests), the flexibility of the layer 160 may relieve stresses that might otherwise occur due to the differences in the CTE of the bumped die 10 and the test carrier 100 . Depending upon the anisotropically conductive materials used, the anisotropically conductive layer 160 may advantageously expand and contract during such testing to prevent delamination or other damage to the bumped die 16 or the test carrier 100 , or to prevent damage from occurring at the connection between the solder bumps 16 and the bond pads 14 .
An additional advantage of the anisotropically conductive layer 160 is that satisfactory electrical contact may be achieved between the contact pads 104 and the solder bumps 16 despite the variation in the heights of the solder bumps 16 . Because the tallest solder bumps 16 become embedded in the layer 160 , if the layer 160 is properly sized, even the shortest solder bumps 16 may be brought into contact with the layer 160 to form an electrical path 166 between the solder bumps 16 and the contact pads 104 . The anisotropically conductive layer 160 may therefore improve the electrical connection between the short solder bumps and the contact pads.
The anisotropically conductive layer 160 may also reduce the compression force needed to bring the short solder bumps 16 into electrical contact with the contact pads 104 . Because the compression force is reduced, the potential for damaging the bumped die 10 or the test carrier (or printed circuit board) 100 is reduced.
Yet another advantage of the anisotropically conductive layer 160 is that the solder bumps 16 of the bumped die 10 may be easily cleaned of any residual amounts of the anisotropically conductive material following testing. Some anisotropically conductive materials are commercially available that are readily dissolvable using solvents for ease of removal and cleanup. One solvent that may be suitable (depending upon the anisotropically conductive material used) is RS 816 available from AI Technology, Inc. of Princeton, N.J. Thus, the time consuming task of flux cleaning associated with traditional soldering may be avoided.
FIG. 5 is a partial cross-sectional view of the bumped die 10 of FIG. 1 engaged with a test carrier 100 b in accordance with an alternate embodiment of the invention. In this embodiment, the test carrier 100 b includes an anisotropically conductive layer 160 b that has a flexible outer surface 168 . The flexible outer surface 168 may be formed, for example, by at least partially curing the anisotropically conductive layer 160 b prior to engagement with the bumped die 10 . The flexible outer surface 168 may be a resilient surface.
To test the bumped die 10 using the test carrier 100 b , the die is positioned over the layer 160 b with the solder bumps 16 approximately aligned with the contact pads 104 . The solder bumps 16 are then compressed against the flexible outer surface 168 causing localized compression of the anisotropically conductive material 160 b in the region near each of the solder bumps 16 . The conductive particles 162 are brought into contact by the compression forces to form the conductive paths 166 between each of the solder bumps 16 and the corresponding contact pads 104 . Test signals are then transmitted to the bumped die 10 through some of the test leads 104 and the conductive paths 166 , and output signals from the bumped die 10 are transmitted from the solder bumps 16 through the conductive paths 166 to the test carrier 100 b as previously described above.
After the bumped die 10 has been tested, it is disengaged from the test carrier 100 b by simply moving the solder bumps 16 away from the flexible outer surface 168 of the anisotropically conductive layer 160 b . If the flexible outer surface 168 of the layer 160 b is a resilient surface, the localized compression areas near each of the solder bumps 16 will spring back to their uncompressed shape.
The test carrier 100 b having the layer 160 b with the flexible outer surface 168 may further improve the process of testing of the bumped die 10 by reducing or eliminating the time and effort involved in detaching the solder bumps 16 from the anisotropically conductive layer 160 b . Because the solder bumps 16 are not embedded in the layer 160 b , it is not necessary to reheat the bumped die 10 or the test carrier 100 b to the rework temperature of the anisotropically conductive layer 160 b in order to disengage the die from the test carrier. The time, effort, and expense associated with disengaging the solder bumps 16 from the anisotropically conductive layer 160 may therefore be reduced or eliminated.
Similarly, because the solder bumps 16 are not embedded in the anisotropically conductive layer 160 b , the time, effort, and expense associated with cleanup of any residual anisotropically conductive material deposited on the solder bumps 16 may also be reduced or eliminated. Depending upon the anisotropically conductive material used, the transfer of material to the solder bumps 16 may be minimized or eliminated so that the solder bumps 16 may be clean enough for immediate use after testing.
FIG. 6 is a partial cross-sectional view of the bumped die 10 engaged with a test carrier (or printed circuit board) 200 in accordance with another alternate embodiment of the invention. In this embodiment, the test carrier 200 includes a test substrate 202 having a plurality of pockets 244 disposed therein. A plurality of test leads 206 are formed on the test substrate 202 , each test lead 206 terminating in a contact pad 204 that is formed within each of the pockets 244 . An anisotropically conductive layer 260 is formed on the test substrate (or printed circuit board) 202 covering the contact pads 204 and test leads 206 . The anisotropically conductive layer 260 includes a plurality of conductive particles 262 contained with a suspension medium 264 , and an outer surface 268 .
In operation, the solder bumps 16 of the bumped die 10 are at least partially disposed within the pockets 244 of the test carrier 200 . The solder bumps 16 may be embedded in the anisotropically conductive layer 260 prior to the curing of the layer, or alternately, the layer 260 may be at least partially cured so that the outer surface 268 is a flexible surface and the solder bumps 16 do not penetrate the outer surface 268 or become attached to the layer 260 . In either case, a compression force may be applied to the bumped die 10 (or to the test carrier 200 ) to compress the anisotropically conductive material to form a conductive path 266 between each solder bump 16 and each contact pad 204 . Testing may then be performed on the bumped die 10 . After testing is complete, the bumped die 10 may be disengaged from the test carrier 200 in one of the ways described above. Alternately, in the case of the bumped die 10 being attached to the printed circuit board 200 , the bumped die 10 is not disengaged.
The test carrier 200 having the pockets 244 and the anisotropically conductive layer 260 further improves the testing of the bumped die 10 by providing the desired electrical contact between the solder bumps 16 and the contact pads 204 without penetration of the solder bumps 16 using contact blades 48 or the like (see FIG. 2 ). Despite the variability of the size and shape of the solder bumps 16 , the anisotropically conductive layer 260 provides the necessary electrical contact along the conductive paths 266 between the solder bumps 16 and the contact pads 104 . Because the contact blades 48 may be eliminated, fabrication and maintenance of the test carrier 200 is simplified compared to the prior art test carrier 40 shown in FIG. 2 . Also, the potential for the solder bumps 16 to be cracked, chipped, or otherwise damaged due to penetration by the contact blades 48 is eliminated.
Similarly, when the bumped die 10 is engaged with the printed circuit board 200 having pockets 244 and the anisotropically conductive layer 260 , the electrical contact between the bumps 16 and the contact pads 204 is improved. As shown in FIG. 6, electrical contact between the solder bumps 16 and the sidewalls 204 is achievable over a larger contact area due to the anisotropically conductive layer 260 , providing improved electrical contact compared with the contact blades 48 of the prior art device (FIG. 2 ). Also, because the contact blades 48 may be eliminated, the manufacturing the pockets 244 is simplified. The pockets 244 may be formed, for example, by masking the areas surrounding the locations of the pockets 244 with a hard mask, and then etching the substrate using an etchant (e.g. KOH).
FIG. 7 is a partial cross-sectional view of the bumped die 10 engaged with a test carrier (or printed circuit board) 300 in accordance with yet another embodiment of the invention. In this embodiment, the test carrier 300 includes a test substrate 302 having a plurality of pedestals 364 projecting upwardly therefrom. Test leads 306 are formed on the test substrate 302 , each test lead 306 terminating in a contact pad 304 formed on at the top of each pedestal 364 .
A magnet 380 having a north pole 382 and a south pole 384 is positioned near the test substrate 302 . A plurality of magnetic flux lines 386 (only two shown in FIG. 7) emanate from the magnet 380 . An anisotropically conductive layer 360 having a plurality of conductive particles 362 and an outer surface 368 is formed on the test substrate 302 . An optical alignment system 390 (such as the type of alignment apparatus shown and described in U.S. Pat. No. 4,899,921 to Bendat et. al.) is positioned proximate the solder bumps 16 to ensure the alignment of the solder bumps 16 with the contact pads 304 . A die handler 392 is engaged with and controllably positions the bumped die 10 . Numerous types of die handlers 392 are suitable for this purpose, including, for example, those shown and described in U.S. Pat. No. 5,184,068 to Twigg et. al., U.S. Pat. No. 5,828,223 to Rabkin et. al., and the IC handlers available from Verilogic Corporation of Denver, Colo.
During the formation of the anisotropically conductive layer 360 , the conductive particles 362 align with the magnetic flux lines 386 to form conductive columns along the flux lines which form a conductive path 366 between each solder bump and its corresponding contact pad. If the magnetic flux lines 386 are strong enough, some of the conductive particles 362 may be induced to protrude from the surface 368 of the layer 360 (as shown in FIG. 7 ). Suitable anisotropically conductive materials that form conductive paths 366 when exposed to a magnetic field include, for example, the Elastomeric Conductive Polymer Interconnect (ECPI) materials available from AT&T Bell Laboratories of Murray Hill, N.J. For testing of the bumped die 10 , the solder bumps 16 may either be embedded in the anisotropically conductive layer 360 prior to the curing of the layer, or alternately, the layer 360 may be at least partially cured so that an outer surface is a flexible surface that is not penetrated by the solder bumps 16 . In either case, the solder bumps 16 are engaged with the anisotropically conductive layer 360 using the die handler 392 and the optical alignment system 390 so that each of the solder bumps 16 are electrically coupled to a corresponding one of the contacts pads 304 by at least one of the conductive paths 366 . Testing may then be performed on the bumped die 10 , and the bumped die 10 may be disengaged from the test carrier 300 in one of the ways described above.
An advantage of the test carrier 300 having the pedestals 364 and the anisotropically conductive layer 360 is that the desired electrical contact between the solder bumps 16 and the contact pads 304 is provided without penetration of the solder bumps 16 using the projections 69 (see FIG. 3 ). Because the projections 69 may be eliminated, fabrication of the test carrier (or printed circuit board) 300 is simplified compared to the prior art test carrier 60 shown in FIG. 3 . Also, the potential for the solder bumps 16 to be cracked, chipped, or otherwise damaged due to penetration by the projections 69 is eliminated.
Another advantage is that the bumped device 10 may be engaged with the test carrier 300 , tested, and disengaged rapidly and efficiently. The anisotropically conductive layer 360 eliminates the time and expense associated with reflowing the solder bumps 16 , and provides the desired electrical contact despite variation in the heights of the solder bumps 16 .
Although the above described embodiments of the anisotropically conductive layers have been described with specific reference to anisotropically conductive materials that form electrically conductive paths when subjected to a compression force, some anisotropically conductive materials do not require a compression force to form conductive paths. For such materials, the desired electrical contact between the solder bumps and the contact pads of the test carrier may be formed without applying a compression force.
Suitable anisotropically conductive materials that do not require a compression force to form conductive paths include, for example, Elastomeric Conductive Polymer Interconnect (ECPI) materials available from AT&T Bell Laboratories of Murray Hill, N.J. Conductive paths are formed in AT&T Bell's ECPI materials by subjecting the materials to a magnetic field.
The detailed descriptions of the above embodiments are not exhaustive descriptions of all embodiments contemplated by the inventors to be within the scope of the invention. Indeed, persons skilled in the art will recognize that certain elements of the above-described embodiments may variously be combined or eliminated to create further embodiments, and such further embodiments fall within the scope and teachings of the invention. It will also be apparent to those of ordinary skill in the art that the above-described embodiments may be combined in whole or in part with prior art apparatus and methods to create additional embodiments within the scope and teachings of the invention.
Thus, although specific embodiments of, and examples for, the invention are described herein for illustrative purposes, various equivalent modifications are possible within the scope of the invention, as those skilled in the relevant art will recognize. The teachings provided herein of the invention can be applied to other apparatus and methods of testing and assembling bumped devices using anisotropically conductive layers, and not just to the apparatus and methods described above and shown in the figures. In general, in the following claims, the terms used should not be construed to limit the invention to the specific embodiments disclosed in the specification and the claims, but should be construed to include all apparatus and methods of testing and assembling bumped devices using anisotropically conductive layers that operate within the broad scope of the claims. Accordingly, the invention is not limited by the foregoing disclosure, but instead its scope is to be determined by the following claims.
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The present invention is directed toward apparatus and methods of testing and assembling bumped die and bumped devices using an anisotropically conductive layer. In one embodiment, a semiconductor device comprises a bumped device having a plurality of conductive bumps formed thereon, a substrate having a plurality of contact pads distributed thereon and approximately aligned with the plurality of conductive bumps, and an anisotropically conductive layer disposed between and mechanically coupled to the bumped device and to the substrate. The anisotropically conductive layer electrically couples each of the conductive bumps with a corresponding one of the contact pads. In another embodiment, an apparatus for testing a bumped device having a plurality of conductive bumps includes a substrate having a plurality of contact pads distributed thereon and substantially alignable with the plurality of conductive bumps, and an anisotropically conductive layer disposed on the first surface and engageable with the plurality of conductive bumps to electrically couple each of the conductive bumps with a corresponding one of the contact pads. Alternately, the test apparatus may also include an alignment device or a bumped device handler. In another embodiment, a method of testing a bumped device includes engaging a plurality of contact pads with an anisotropically conductive layer, engaging the plurality of conductive bumps with the anisotropically conductive layer substantially opposite from and in approximate alignment with the plurality of contact pads, forming a plurality of conductive paths through the anisotropically conductive layer so that each of the conductive bumps is electrically coupled to one of the contact pads, and applying test signals through at least some of the contact pads and the conductive paths to at least some of the conductive bumps.
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BACKGROUND OF THE INVENTION
This invention relates generally to moldings, and particularly to a composite, convertible, laminable molding for use as railings, balustrades, parapets and other decorative as well as functional uses.
Decorative moldings have been used throughout the ages for various functional as well as decorative purposes, such as for railings, balustrades, parapets and other applications where they have been considered particularly appropriate and pleasing in appearance. In fact, the use of decorative moldings has been so wide and varied that the sizes, shapes, appearances of the moldings used have been numerous and limited only by the imagination of their creators. In the past, these moldings have been carved from wood in sizes and configurations according to the requirements of the user and in more recent times mass-produced in particular configurations and sizes for use by those whose tastes may coincide with the manufacturer's.
In recent years, developments have also been made in convenient metallic structures for railings, composite railings with wood and metal parts, as well as specific developments directed to methods and apparatus for attaching moldings to brackets such as for use in safety railings for stairwells. U.S. Pat. No. 3,482,819, issued to G. Laurent, shows stairway railings and the like which are fabricated from interlocking extruded metallic channel members. Elongated pairs of U-shaped elements are arranged to interlock on a slide-on or clip-on type of arrangement to form upper and lower railings. Balustrades are interconnected via tongue-and-groove attachments, and a cover cap is also snapped or slide-connected to the top. U.S. Pat. No. 3,289,381, issued to L. Blum et al, discloses an elongated wood member which is tongue-and-groove attached to an elongated mating metallic base member with screws being used to retain the sandwiched assembly. U.S. Pat. No. 3,804,374, issued to W. Thom, is of interest to the extent of its disclosure of an elongated rail cap which is tongue-and-groove attached to retaining posts. U.S. Pat. Nos. 3,356,392, issued to L. Blum et al, and 3,358,869, issued to E. W. Palmer et al are of general interest for their disclosure of plug-in type end caps for use with tubing or laminated railing structures.
Although these prior art patents are of interest and are probably successful for the particular purposes for which they were designed, it has been found desirable to advance beyond the moldings heretofore known and used and to develop molding structures comprised of a plurality of individual components which can be mass-produced and then assembled with some latitude in creativity by professionals and novices alike in constructing moldings for selective functional as well as aesthetic purposes.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide standard, interengageable, elongated molding members which can be selectively mated together in laminar fashion and unified into desired thickness and design for use in assembling railings, balustrades, parapets and the like.
It is another object of the present invention to provide convertible or interchangeable members with different characteristics and appearances but with interfitting parts so that said members can be interfittingly laminated together in a variety of combinations to construct moldings with individually desired characteristics of size, shape, and appearance.
It is also an object of the present invention to provide a composite molding structure comprised of individual members with mating engagement means to provide structural rigidity and finishing members for concealing the engagement means to provide an integrated appearance.
It is a further object of the present invention to provide individual members of a composite molding structure, identical members of which can be laminated together to achieve the desired size and appearance together with an interfitting key fillet member for providing structural rigidity to the finished molding.
It is a still further object of the present invention to provide individual components which can be laminated together to be interchangeably used to develop a finished molding of desired size with finishing cap members not only to conceal the interfitting means but also to provide a contoured surface for a comfortable fit and feel as well as effective grasp by a person's hand.
The present invention includes a plurality of elongated structural members with matingly engageable interfitting means and with ornamental as well as functional configurations which can be laminated together in a variety of combinations to build up composite molding structures of desired sizes and shapes. Interfitting or mating means are comprised primarily of strategically sized and located mating channels and elongated, rectilinear tongues or ribs, as well as fillets and cap members with contoured surfaces to impart a finished appearance and feel. The elongated rectilinear ribs are dimensioned and sized to snugly fit within correspondingly sized and shaped mating channels of adjacent laminated members to provide structural rigidity to the finished molding.
The individual molding members are thus conveniently designed for use by amateurs as well as professionals in constructing composite moldings, and the various configurations with mating interfitting means are conducive to allowing one to exercise his creativity in interchangeably utilizing different individual members in constructing composite moldings of a variety of sizes and configurations according to individual tastes and needs.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects, advantages and capabilities of the present invention will become more apparent as the description proceeds, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a perspective view of a balustrade comprised of railings assembled in accordance with the present invention and supported by balusters;
FIG. 2 is an exploded, cross-sectional view of the principal structural members of the present invention;
FIG. 3 is a perspective view of a segment of a composite molding comprised of a combination of structural members in accordance with the present invention;
FIG. 4 is a perspective view of the structural members laminated together in a variation to form a different molding configuration;
FIG. 5 is a perspective view of the structural members laminated together in still another variation with a fillet member in the bottom for a finished appearance;
FIG. 6 illustrates another combination in which the different structural members and caps can be arranged in combination with a baluster;
FIG. 7 shows still another variation in which identical structural members are laminated together and interfitted with a fillet key member, and also showing the upper end of a baluster engaged in the interfitting means of a structural member; and
FIG. 8 is a perspective view of a segment of the structural members laminated together in still another variation, and also showing an alternate embodiment of the interfitting means.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A balustrade 10 with moldings or railings 20, 22, and 24 constructed in accordance with the present invention and supported by balusters 12 and 16 is shown in FIG. 1. The present invention is directed to convertible or interchangeable elements can be laminated together in different combinations into a variety of desirable sizes and configurations such as those shown in FIG. 1 at 20, 22, and 24. The elements are preferably fabricated from wood, although other materials such as metal would also be suitable in some applications.
The cross-sectional forms of the principal structural members can best be seen in FIG. 2 wherein a cap member 26, a body 40 with longitudinal convex ridges 41 along its opposite lateral edges, another body member 50 with concave longitudinal grooves 51 along opposite lateral edges, and a larger cap member 30 are shown in exploded relation to illustrate the respective configurations as well as those features which comprise the interfitting or mating means whereby the respective structural members can be laminated together into unitary relation for added structural strength.
The body member 40 has a convex ridge 41 extending longitudinally on each lateral side of the body member and two elongated rectilinear tongues or ribs 42 protruding upwardly, each having a flat upper surface 48 and respective parallel inside faces 44 in spaced-apart relation to each other forming a channel 43 between said spaced-apart inside faces 44. The body member 40 also has two elongated rectilinear ribs 45 protruding downwardly with flat lower surfaces 49 and parallel inside faces 47 in spaced-apart relation to each other forming a channel 46 therebetween. Each upper rib 48 also has an outside face 44', and each lower rib has an outside face 47'. The channels 43 and 46 are of equal width and depth and the inside faces 44 lay in the same respective planes as the inside faces 47. Also, the widths of ribs 42 and 49 are all equal so that the outside faces 44' and 47' on each side of the body member 40 lie in respective common planes.
The body member 50 has lateral sides with longitudinal concave grooves 51, upwardly directed lips or ribs 52 and downwardly directed lips or ribs 55. The upwardly directed lips 52 define a common channel 53 therebetween with inside faces 54 in parallel spaced-apart relation to each other. Likewise, the downwardly directed lips 55 define a common channel 56 therebetween with inside faces 57 in parallel spaced-apart relation to each other. The inside faces 54 and 57 on each side of the body member 50 lie in common respective planes. Also, the spacing between the inside faces 54 and the inside faces 57 approximately the distances between the outside faces 44' and 47', respectively, of body member 40.
It can thus be appreciated that body member 40 can be laminated together in interfitting, material relationship with body member 50 such as by inserting ribs 45 of body member 40 between lips 52 of body member 50. The thickness of ribs 42 and 45 is approximately equal to the depth of channels 53 and 56 so that when body members 40 and 50 are laminated together as described above, the flat surfaces 49 contact the flat surface of channel 53 and the outside faces 47' contact the inside faces 54. It can thus be appreciated that body members 40 and 50 can be securely retained together for example by gluing these contacting surfaces of the respective body members together or by nailing or screwing in a conventional manner.
FIG. 2 also shows a cross-sectional view of an elongated cap member 26 disposed directly above the convex ribbed body member 40. The cap member 26 has a flat underside 28, parallel spaced-apart lateral surfaces 27 which are oriented perpendicular to the flat underside 28, and a contoured upper surface 29 of a generally flattened V-shaped cross-section. The overall width of the cap member 26, i.e., the distance between lateral surfaces 27, corresponds to the distance between inside faces 44 of body member 40. It can thus be appreciated that the cap member 26 is sized to be received within the channel 43 to conceal the interfitting means of body member 40 and to provide a contoured, finished appearance for the upper surface of a rail constructed with a body member 40. Cap member 26 can be permanently retained in channel 43 with appropriate fasteners, such as glue, nails, or screws.
A larger cap member 30 is also shown in cross-section in FIG. 2 with a flat underside 32 and perpendicularly disposed lateral surfaces 31, as well as a larger contoured surface 33 of generally V-shaped configuration. The distance between lateral surfaces 31 corresponds with the distance between inside faces 57 of the concave grooved body member 50. Thus, as seen from FIG. 2, the larger cap member 30 can be received within the channel 56 of body member 50 to conceal the interfitting means and to provide a contoured, finished appearance. Cap member 30 can also be permanently fixed in channel 56 with glue, nails, screws and the like.
The perspective view of FIG. 3 illustrates the body members 40 and 50 and the cap members 26 and 30 in assembled, laminated relation to each other. The view in FIG. 3 shows these members assembled in a finished molding with a pleasing architectural appearance on the lateral sides with comfortable, contoured upper and lower surfaces. It is also noted that in this embodiment, the thickness of the lateral surfaces 27 of cap member 26 exceeds the depth of channel 43 leaving a portion of the lateral surfaces 27 exposed to impart an additional architectural break as a feature in the appearance of the finished molding as indicated at 61. A similar break in the contoured surface for aesthetic purposes is provided in this embodiment by the lateral surfaces 31 of the larger cap member 30 being somewhat thicker than the depth of channel 56 in body member 50 as shown at 62.
The perspective view in FIG. 4 discloses another variation in the arrangement of the body and cap members to provide a somewhat thicker handrail with a different architectural appearance on the lateral sides of the molding. In this view, a body member 40 which the longitudinal convex ridges 41 and extending ribs 48, 49 is sandwiched between two body members 50 with the longitudinal concave grooves 51 and extending lips 52, 55. Two larger cap members 30 are used in this configuration, one to provide a contoured surface on the upper side of the finished molding and the other to provide a contoured surface on the lower side of the finished molding. This view also illustrates an additional variation in the cap members 30 which are still generally thicker than the depth of the channels 53 and 56 of body members 50; however, the outer portions of lateral surfaces 31 are rounded as indicated at 63 to eliminate the sharpness which was apparent in the embodiment shown in FIG. 3 at 61 and 62.
FIG. 5 illustrates an arrangement similar to that shown in FIG. 4 with a body member 40 with longitudinal convex ridges sandwiched between two body members 50 with longitudinal concave grooves. This configuration, however, also illustrates another variation in providing a finished appearance by inserting a flat surfaced fillet 34 into the channel 56 of the lower body member 50. As can be seen in FIG. 5, the fillet 34 completely fills the channels 56 providing a flat, finished appearance for the underside of the molding. This configuration is particularly appropriate for use as a handrail wherein the mounting bracket may require a flat undersurface on the rail for fastening. The filler 34 can be permanently retained in place by nails, screws or glue.
The configuration in FIG. 5 also shows another variation in the larger cap member 30. In this variation the lateral surfaces 31 are of the same thickness as the depth of channel 53 in the upper body member 50, resulting in a continuously smooth joint between the lips 52 of body member 50 and the contoured surface 33 of cap member 30 as indicated at 64.
FIG. 6 illustrates a perspective view of the concave lipped body member 50 in overlaying, interfacing relation to convex ribbed body member 40. A large contoured cap member 30 is also shown in this arrangement to provide a finished top surface as well as illustrating the upper end 17 of a supporting baluster 16 matingly received within the channel 46. Further, FIG. 6 illustrates another form of convex ribbed body member 40 having rounded external edges on the ribs 48, 49 as indicated at 66 for a smoother appearance and feel.
The perspective view in FIG. 7 indicates still another variation in combining two similar convex ribbed body members 40 in adjacent laminar relationship resulting in a somewhat different architectural appearance of the sides of the finished moldings. When two convex ribbed body members 40 are laminated together in the manner shown in FIG. 6, the thicker fillet 37 with a rectangular cross-sectional configuration serves as a key to provide a mating engagement between the like interfitting means of two body members 40. In this combination, the key fillet 37 has a thickness which approximates the sum of the depths of the respective channels 43 and 46 in adjacent body members 40 to substantially fill the interstice between the two body members. It can be appreciated that this same principle can also be applied to interfittingly stack two concave lipped body members 50 in adjacent laminar fashion if so desired. This combination is also shown with smaller cap member 26 with lateral surfaces 27 of equal thickness to the depth of channel 43 of the upper body member 40 to provide a continuous joint between the flat surface 48 of rib 42 and the contoured surface 29 of cap member 26 as indicated at 65.
The views in FIGS. 1, 6, and 7 considered together are instructive on methods and configurations which are appropriate for constructing a balustrade. FIGS. 6 and 7 illustrates how a baluster 16 with an upper top portion 17 of substantially square crosss-sectional configuration can be matingly joined with a convex ribbed body member 40 by inserting the top portion 17 into the channel 46 of body member 40. Referring again to FIG. 1, the lower and middle moldings 24 and 22 respectively, are each comprised substantially of a single concave lipped body member 50. The upper molding or railing is comprised of substantially a single body member 50 with a larger cap member 30 to provide a contoured upper surface. On the lower end, the lower portions 15 of balusters 12 are interfittingly engaged with the body member 50 by insertion into channel 53. The upper portions 13 of balusters 12 are likewise matingly engaged with the body member 50 of middle molding 22 by insertion into the channel 56. The shorter balusters 16 are similarly matingly engaged with the middle railing 22 and the upper railing 20 by inserting the lower portions 19 and upper portions 17 into the respective channels of the respective body members 50.
Then, both to provide additional structural integrity as well as interfitting engagement between the balusters and the moldings and to provide a pleasing, finished appearance concealing the interfitting means of the body member, fillets 34 are placed in the channels 53 and 56 of body member 50. It can be appreciated that when all of these elements are fastened together such as by nailing, screwing, or gluing, a relatively strong balustrade with a pleasing appearance can be constructed. It can also be appreciated that one can use his individual creativity to assemble railings and moldings of various sizes and configurations as already discussed, as well as numerous other variations which have not been discussed but which are implicit in this invention.
Although it is recognized that the main body members could be fabricated with virtually an infinite number of sizes and side configurations, the longitudinal convex ridge 41 of body member 40 and the longitudinal concave grooves 51 of body member 50 have been illustrated in this preferred embodiment because they have been found to be particularly appropriate for use in hand rails and balustrades. Two adjacent convex ridges 41 as illustrated in FIG. 7 or any combination of concave grooves 51 alone or in combination with convex ridges 41 as illustrated in FIGS. 1, 3, 4, 5, and 6, have been found to be especially appropriate and comfortable for use in handrails where the ends of a person's fingers grasp the resulting contours of the lateral sides of the moldings. The contoured cap members 26 and 30 with flattened V-shaped cross-sectional configurations have also been found to be particularly appropriate for use in handrails since they provide a confortable fit for the palm of a person's hand.
An alternative embodiment is illustrated in FIG. 8 wherein the same general side configurations for main body members are used but in which a variation in the interfitting means is used. A body member 70 with a longitudinal convex ridge 71 along its lateral sides with extending ribs 72 is shown in the lower laminated position in a molding. A body member 80 with longitudinal concave grooves 81 and extending lips or ribs 82 is shown in the upper laminated position in this molding configuration. The convex ribber body member 70 is also provided with channels 73, inside faces 74, and outside faces 75. The convex ribbed body member 80 is also provided with channels 83 and inside faces 84.
As described in the preferred embodiment, these respective features are sized and spaced for interfitting, mating engagement with one another, except that in this embodiment, the outside and inside faces 75, 74, and 84, respectively, rather than laying in common planes, are slanted at acute angles with respect to the channels 73 and 83. Accordingly, the body members are matingly engaged in laminar fashion by sliding the respective interfitting means together in longitudinal fashion. The actual process of laminating the body members together is therefore not as easy and quick as described in the preferred embodiment; however, once these body members are interfitted together as shown in FIG. 8, the engagement is more positive with resultant increased structural integrity.
Also, as shown in FIG. 7, the cap member 90 with contoured surface 91 in the form of a flattened V-shaped cross-section is also provided with lateral surfaces 93 disposed at an acute angle to the underside 92 to correspond to the acute angles of the interfitting means of concave lipped body member 80. Fillet 95 is similarly provided with lateral surfaces 97 at acute angles to the underside 96 corresponding to the acute angles of the interfitting means of convex ribbed body member 70.
Although the present invention has been described with a certain degree of particularity, it is understood that the present disclosure has been made by way of example and that changes in details and structure may be made without departing from the spirit thereof.
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A composite molding structure combines a plurality of laminated body members with matingly engageable channels and extensions sized and shaped to at least partially interfittingly retain said body members from movement relative to one another, and filling and finishing members are so constructed and arranged as to conceal said channels and extensions whereby to impart a finished, contoured appearance and feel. The body members also include a variety of distinctive architectural configurations on their lateral sides which serve both as functional gripping surfaces as well as to impart an ornamental appearance to the finished molding. The various shapes and configurations with corresponding engagement means are conducive to the exercise of one's individual creativity in laminating various members together in a variety of combinations to produce finished moldings, handrails, balustrades and the like of desired size and appearance.
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BACKGROUND OF THE INVENTION
1. Field of The Invention
The invention concerns a method for synthesizing gem-difluorinated C-glycopeptide compounds. It applies in particular, but not exclusively, to the preparation of compounds or compositions usable notably in the preservation of biological materials and in cryosurgery.
2. Description of The Prior Art
Antifreeze biological compounds exist in the natural environment, glycoproteins in particular. These are compounds present for example in some fishes, enabling them to survive in a low-temperature environment, i.e. near zero or sub-zero temperatures.
Also, it is known that when water freezes, this phenomenon is accompanied by a volume increase due to the three-dimensional growth of ice.
This increase, and resulting osmosis, cause serious damage in living tissues: cell membranes are ruptured, blood ceases to flow and cell microstructures are disturbed.
For many years, scientists have been investigating how antifreeze compounds taken from the natural environment (fish, amphibians, plants, insects . . . ) have an influence on these phenomena, these compounds being notably proteins and glycoproteins.
Intensive research is focusing on the synthesis of similar compounds that are sufficiently stable and whose activity is at least equal to or even greater than the activity of the natural molecules, for commercial applications.
Due to the presence of an osidic bond (bond involving oxygen said to be in an anomeric position) glycoproteins are fragile relatively to several enzymatic systems, including glycosidase enzymes, and are also sensitive to acid-base hydrolysis making their synthesis more difficult.
It is therefore of interest, in order to allow these compounds to maintain their biological properties, to replace the oxygen in the osidic bond so that this bond is no longer deteriorated by an enzymatic process.
Analogs, in which oxygen is replaced by a CH 2 group, have been synthesized, but despite an increase in stability and a steric hindrance similar to that of oxygen, the CH 2 group has not always proved to be a good mimic of osidic oxygen. Consequently, the biological properties of the initial compound are not always found.
Other classes of compounds in which oxygen is replaced by a nitrogen or sulphur and more recently by a difluoromethylene group are being researched with a view to imparting increased stability to glycoconjugate compounds in a biological medium.
The CF 2 group shows particular resistance to processes of biochemical degradation and therefore allows the synthesis of non-hydrolysable structures.
This O/CF 2 transposition seems to be especially well adapted to mimicking oxygen at electronic level; the two fluorine atoms acting as the two oxygen-free doublets.
Said compounds could possibly be used for numerous applications such as the preservation of cells, blood platelets, tissues, organs, or for cryosurgery.
There exists a strong demand for an improvement in the storage and preservation of irreplaceable living cells, including sperm, ovules and embryos so that they undergo much less damage than with methods currently used.
The term preservation generally includes preservation at different temperatures, including cryopreservation down to temperatures as low as −196° C.
Therefore, compounds used as adjuvants for preservation and having good stability could be useful for preserving biological materials, notably:
for storing whole human organs such as kidneys, hearts and livers to be transplanted under no time constraints, for preserving delicate tissues with minimum damage and for a sufficiently long period to allow optionally international distribution, for preserving blood platelets and cells, for protecting certain organisms, bacteria, viruses or vaccines.
Cryosurgery, also called cryotherapy, is the use of extreme cold produced by liquid nitrogen (or argon gas) to destroy abnormal tissues.
It is used to treat external tumours such as skin tumours but is also used to treat tumours inside the body, notably in the prostate and liver. Researchers have tested cryosurgery as a treatment for a certain number of cancers including breast cancer, colon and kidney cancers.
In addition, some studies have reported that at a certain concentration (5-10 mg/ml), antifreeze glycoproteins and proteins produce spicule-shaped ice crystals which increase the probability of cell rupture and death during freezing. This property of ice crystals modified by antifreeze glycoproteins and proteins finds applications of high interest in the treatment of some cancers, if they are used in conjunction with cryosurgery.
OBJECT OF THE INVENTION
On this basis, the object of the invention is to solve the above-cited drawbacks.
SUMMARY OF THE INVENTION
For this purpose, it proposes a gem-difluorinated C-glycopeptide having the general formula I:
in which:
N is an integer between 1 and 5, R 4 =H, AA 1 , AA 1 -AA 2 , R 5 =OH, AA 1 , AA 1- AA 2 , AA 1 and AA 2 are independents and representing amino acids with a non-functionalised side chain and R 1 , R 2 , R 3 are independent groups and if R 1 =R 2 =H, CH 3 , CH 2 Ph, CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2 , CH(CH 3 )CH 2 CH 3 then R 3 =
in which: n is an integer between 3 and 4,
Y, Y′ are independent groups in which Y, Y′=H, OR, N 3 , NR′R″, SR′″ . . .
where R=H, Bn, Ac, TMS, TBDMS, TBDPS, . . . , R′, R″=H, alkyl, allyl, Bn, tosylate (Ts), C(═O)-alkyl, C(═O)-Bn, . . . , R′″=H, alkyl, Ac,
R 6 is notably a group H, CH 3 , CH 2 OH, CH 2 -Glycoside group, CH 2 —OGP in which GP is a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 7 =OH, OGP′, NH 2 , N 3 , NHGP′, NGP′GP″ in which GP′ and GP″ is or not a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 8 is a hydrogen atom H or a free or protected alcohol function,
if R 1 =R 3 =H, CH 3 , CH 2 Ph, CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2 , CH(CH 3 )CH 2 CH 3
then R 2 =
in which: n is an integer between 3 and 4,
Y, Y′ are independent groups
in which: Y, Y′=H, OR, N 3 , NR′R″, SR′″ . . .
where R=H, Bn, Ac, TMS, TBDMS, TBDPS, . . . , R′, R″=H, alkyl, allyl, Bn, tosylate (Ts), C(═O)-alkyl, C(═O)-Bn, . . . , R′″=H, alkyl, Ac,
R 6 is notably a group H, CH 3 , CH 2 OH, CH 2 -Glycoside group, CH 2 —OGP group in which GP is a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 7 =OH, OGP′, NH 2 , N 3 , NHGP′, NGP′GP″ in which GP′ and GP″ is or not a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 8 is a hydrogen atom H or a free or protected alcohol function,
if R 2 =R 3 =H, CH 3 , CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2 , CH(CH 3 )CH 2 CH 3
then R 1 =
in which: n is an integer between 3 and 4,
Y, Y′ are independent groups
in which Y, Y′=H, OR, N 3 , NR′R″, SR′″ . . .
where R=H, Bn, Ac, TMS, TBDMS, TBDPS, . . . , R′, R″=H, alkyl, allyl, Bn, tosylate (Ts), C(═O)-alkyl, C(═O)-Bn, . . . , R′″=H, alkyl, Ac,
R 6 is notably a group H, CH 3 , CH 2 OH, CH 2 -Glycoside group, CH 2 —OGP in which GP is a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 7 =OH, OGP′, NH 2 , N 3 , NHGP′, NGP′GP″ in which GP′ and GP″ is or not a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 8 is a hydrogen atom H or a free or protected alcohol function.
In the R 4 and R 5 functional groups, the amino acids AA 1 and AA 2 are amino acids with a non-functionalised side chain, i.e. non-polar such as Glycine, Alanine, Valine, Leucine, Isoleucine, Phenylalanine . . . .
In the R 6 functional group, the glycoside may be any sugar such as glucose, galactose, mannose, . . . .
According to one variant, a gem-difluorinated C-glycopeptide compound of the invention may be of formula II:
in which: N is an integer between 1 and 5,
and R 1 , R 2 , R 3 are independent groups and if R 1 =R 2 =H, CH 3 , then R 3 =
in which: n is an integer between 3 and 4,
Y, Y′ are independent groups
In which Y, Y′=H, OR, N 3 , NR′R″, SR′″ . . .
where R=H, Bn, Ac, TMS, TBDMS, TBDPS, . . . , R′, R″=H, alkyl, allyl, Bn, tosylate (Ts), C(═O)-alkyl, C(═O)-Bn, . . . , R′″=H, alkyl, Ac,
R 6 is notably a group H, CH 3 , CH 2 OH, CH 2 —OGP in which GP is a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 7 =OH, OGP′, NH 2 , N 3 , NHGP′, NGP′GP″ in which GP′ and GP″ is or not a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 8 is a hydrogen atom H or a free or protected alcohol function,
if R 1 =R 3 =H, CH 3 ,
then R 2 =
in which: n is an integer between 3 and 4,
Y, Y′ are independent groups
In which Y, Y′=H, OR, N 3 , NR′R″, SR′″ . . .
where R=H, Bn, Ac, TMS, TBDMS, TBDPS, . . . , R′, R″=H, alkyl, allyl, Bn, tosylate (Ts), C(═O)-alkyl, C(═O)-Bn, . . . , R′″=H, alkyl, Ac,
R 6 is notably a group H, CH 3 , CH 2 OH, CH 2 —OGP in which GP is a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 7 =OH, OGP′, NH 2 , N 3 , NHGP′, NGP′GP″ in which GP′ and GP″ is or not a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 8 is a hydrogen atom H or a free or protected alcohol function,
if R 2 =R 3 =H, CH 3 ,
then R 1 =
in which: n is an integer between 3 and 4,
Y, Y′ are independent groups
In which Y, Y′=H, OR, N 3 , NR′R″, SR′″ . . .
where R=H, Bn, Ac, TMS, TBDMS, TBDPS, . . . , R′, R″=H, alkyl, allyl, Bn, tosylate (Ts), C(═O)-alkyl, C(═O)-Bn, . . . , R′″=H, alkyl, Ac,
R 6 is notably a group H, CH 3 , CH 2 OH, CH 2 —OGP in which GP is a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate group (Ac), R 7 =OH, OGP′, NH 2 , N 3 , NHGP′, NGP′GP″ in which GP′ and GP″ is or not a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 8 is a hydrogen atom or a free or protected alcohol function.
According to a second variant, the compound may, more precisely, be of general formula III:
in which:
N is an integer between 1 and 5, n is an integer between 3 and 4, R 7 =OH, OGP′, NH 2 , N 3 , NHGP′, NGP′GP″ in which GP′ and GP″ is or not a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 8 is a hydrogen atom or a free or protected alcohol function, R 9 =H, CH 3 , R 10 =H, CH 3 . R 11 is a hydrogen atom (H) or a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group.
The compounds of general formulas I-III when in the state of a possible pharmaceutically acceptable base, additive salt to an acid, hydrate or solvate and any derivatives thereof may be produced in different galenic forms suitable for use, for example as solutions or suspensions, optionally injectable.
The compounds of general formulas II and III and some compounds of general formula I may be synthesis intermediates for compounds of general formula I.
Some compositions may contain at least one compound of general formula I, II or II or one of its derivatives or one of its salts obtained by addition to a pharmaceutically acceptable mineral or organic acid.
In addition, this compound of general formula I-III may be prepared by a reaction between a compound with general formula IV:
wherein Y, Y′ are independent groups
in which Y, Y′=H, OR, N 3 , NR′R″, SR′″ . . .
where R=H, Bn, Ac, TMS, TBDMS, TBDPS, . . . , R′, R″=H, alkyl, allyl, Bn, tosylate (Ts), C(═O)-alkyl, C(═O)-Bn, . . . , R′″=H, alkyl, Ac,
R 6 is notably a group H, CH 3 , CH 2 OH, CH 2 —OGP in which GP is a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac), CH 2 -Glycoside group, R 7 =OH, OGP′, NH 2 , N 3 , NHGP′, NGP′GP″ in which GP′ and GP″ is or not a protector group such as an alkyl, benzyl (Bn), trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS), acetate (Ac) group, R 8 is a hydrogen atom H or a free or protected alcohol function,
and a compound of general formula V:
wherein N is an integer between 1 and 5,
R 15 =H, AA 1 , AA 1 -AA 2 or a protective group, R 16 =OH, AA 1 , AA 1- AA 2 or a protective group AA 1 and AA 2 are independent groups and representing amino acids with a non-functionalised side chain, And R 12 , R 13 , R 14 are independent groups if R 12 =R 13 =H, CH 3 , CH 2 Ph, CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2 , CH(CH 3 )CH 2 CH 3 then R 14 is —(CH 2 ) n —NH 2 with n is an integer between 3 and 4, if R 12 =R 14 =H, CH 3 , CH 2 Ph, CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2 , CH(CH 3 )CH 2 CH 3 then R 13 is —(CH 2 ) n —NH 2 with n is an integer between 3 and 4, if R 13 =R 14 =H, CH 3 , CH 2 Ph, CH(CH 3 ) 2 , CH 2 CH(CH 3 ) 2 , CH(CH 3 )CH 2 CH 3 then R 12 is —(CH 2 ) n —NH 2 with n is an integer between 3 and 4.
In addition to pharmaceutically acceptable inert, non-toxic excipients such as distilled water, glucose, starch lactose, talc, vegetable oils, ethylene glycol . . . , the compositions so obtained may also contain preserving agents.
Other active ingredients may be added to these compositions.
The quantity of the compound according the invention and other optional active ingredients in said compositions may vary according to application, the age and weight of the patient when applicable.
BRIEF DESCRIPTION OF THE DRAWINGS
Examples of the preparation of compounds of the invention are described below as non-restrictive examples with reference to the accompanying drawings, in which:
FIG. 1 is a reaction equation to obtain compound 3;
FIG. 2 is a reaction equation to obtain compound 5;
FIG. 3 is a reaction equation to obtain compound 1;
FIG. 4 is a reaction equation to obtain compound 7;
FIG. 5 is a reaction equation to obtain compound 9;
FIG. 6 is a reaction equation to obtain compound 10;
FIG. 7 is a reaction equation to obtain compound 12;
FIG. 8 is a reaction equation to obtain compound 13;
FIG. 9 is a reaction equation to obtain compound 14;
FIG. 10 is a reaction equation to obtain compound 15;
FIG. 11 is a reaction equation to obtain compound 16;
FIG. 12 is a reaction equation to obtain compound 19;
FIG. 13 is a reaction equation to obtain compound 21;
FIG. 14 is a reaction equation to obtain compound 22;
FIG. 15 is a reaction equation to obtain respectively compound 23, 24, 25 (SEQ ID NO:1);
FIG. 16 is a reaction equation to obtain compound 26 (SEQ ID NO:1);
FIG. 17 is a reaction equation to obtain compound 12 or 27 (SEQ ID NO:1);
FIG. 18 is a reaction equation to obtain compound 28 (SEQ ID NO:1);
FIG. 19 is a reaction equation to obtain compound 29 (SEQ ID NO:1);
FIG. 20 is a reaction equation to obtain compound 30 (SEQ ID NO:1);
FIG. 21 is a representation of effects of compound 15 on HEK293 viability at 4° C.;
FIG. 22 is a representation of effects of compound 15 on HEK293 viability at 2° C.;
FIG. 23 is a representation of effects of compound 15 on HEK293 viability at 0° C.;
FIG. 24 is a representation of effects of compound 15 on HEK293 viability at −2° C.;
FIG. 25 is a representation of effects of compound 15 on HEK293 viability at −4° C.;
FIG. 26 is a representation of effects of compound 15 on HEK293 viability at −20° C.;
FIG. 27 is a representation of effects of compound 15 on platelet aggregation at 22° C.;
FIG. 28 is a representation of effects of compound 15 on platelet aggregation at 15° C.;
FIG. 29 is a representation of effects of compound 15 on platelet aggregation at 4° C.;
FIG. 30 is a representation of effects of compound 15 (monomer) on preservation of H9c2(2-1) cells at −2° C.;
FIG. 31 is a representation of effects of compound 30 (dimer) on preservation of H9c2(2-1) cells at −2° C.;
FIG. 32 is a representation of a comparison of Monomer 15 vs. Dimer 30 at various time;
FIG. 33 is a representation of viability of heart cells after exposure of 8 Hours with 1 mg/mL of monomer 15 and dimer 30;
FIG. 34 is a representation of viability of heart cells after exposure of 16 Hours with 1 mg/mL of monomer 15 and dimer 30;
FIG. 35 is a representation of viability of heart cells after exposure of 22 Hours with 1 mg/mL of monomer 15 and dimer 30;
FIG. 36 is a representation of viability of heart cells over time at room temperature (22° C.) in presence of 1 mg/mL of monomer 15 and dimer 30;
FIG. 37 is a representation of viability of heart cells over time at 4° C. in presence of 1 mg/mL of monomer 15 and dimer 30;
FIG. 38 is a representation of viability of heart cells over time at −3° C. in presence of 1 mg/mL of monomer 15 and dimer 30;
FIG. 39 is a representation of viability of heart cells over time at −10° C. in presence of 1 mg/mL of monomer 15 and dimer 30;
FIG. 40 is a representation of viability of heart cells over time at 3° C. in presence of 1 mg/mL of monomer 15;
FIG. 41 is a representation of viability of heart cells at 3° C. and 4.4 mM of glycoproteins 15 and 30;
FIG. 42 is a representation of viability of heart cells at −3° C. and 4.4 mM of glycoproteins 15 and 30;
FIG. 43 is a representation of viability of heart cells at −3° C. with increasing concentration of glycoproteins 15 and 30;
FIG. 44 is a representation of viability of skin cells after exposure of 8 hours of 5 mg/mL Monomer 15;
FIG. 45 is a representation of viability of skin cells after exposure of 12 hours of 5 mg/mL Monomer 15;
FIG. 46 is a representation of viability of skin cells after exposure of 20 hours of 5 mg/mL Monomer 15;
FIG. 47 is a representation of viability of skin cells after exposure of 30 hours of 5 mg/mL Monomer 15;
FIG. 48 is a representation of viability of skin cells over time at room temperature (22° C.) in presence of 5 mg/mL Monomer 15;
FIG. 49 is a representation of viability of skin cells over time at 3° C. in presence of 5 mg/mL Monomer 15;
FIG. 50 is a representation of viability of skin cells over time at −3° C. in presence of 5 mg/mL Monomer 15;
FIG. 51 is a representation of viability of skin cells after exposure of 20 hours at increasing concentrations of compound 15;
FIG. 52 is a representation of viability of skin cells after exposure of 34 hours at increasing concentrations of compound 15;
FIG. 53 is a representation of effects of 10 mg/ml of compound 15 on cell viability at 37° C. in low-serum media (Adherent Culture);
FIG. 54 is a representation of effects of 10 mg/ml of compound 15 on cell viability at 15° C. in low-serum media;
FIG. 55 is a representation of cells at Day 1;
FIG. 56 is a representation of effects of 15 mg/ml of compound 15 on cell viability at 15° C. in culture media;
FIG. 57 is a representation of effects of 15 mg/ml of compound 15 on cell viability at 3° C. in culture media;
FIG. 58 is a representation of effects of H 2 O 2 on cells treated with 15 mg/mL of compound 15 at 37° C.;
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The abbreviations used are as follows:
eq.: equivalent
g: gram
Hz: Hertz
mg: milligram
MHz: megaHertz
min.: minute
mL: millilitre
mmol: millimole
μmol: micromole
nmol: nanomole
The characteristics of the instruments used to perform the analyses of all the compounds described in the present application are given below:
1 H, 13 C, and 19 F NMR spectra were recorded on BRUKER DPX 300 and DPX 600 spectrometers. For 1 H and 13 C NMR, tetramethylsilane was used as internal reference. For 19 F NMR the external reference was fluorotrichloromethane CFCl 3 . Chemical shifts are expressed in parts per million (ppm), coupling constants J in Hertz (Hz).
The following abbreviations were used:
s pour singlet, bs for broad singlet, d for doublet, t for triplet, q for quartet, m for multiplet, dd for doublet of doublet . . .
Mass spectra were obtained on a spectrophotometer of the type Micromass TOF-SPEC, E 20 kV, α-cyano. For MALDI ionisation, JEOL AX500, 3 kV, Canon FAB JEOL, Xe, 4 kV, courant limite 10 μA, Gly-NBA 50:50 for FAB ionisation.
Separations by column chromatography were performed under light pressure following chromatography techniques on Kiesel 60 silica gel (230-400 Mesh, Merck).
Follow-up was made by thin-layer chromatography (TLC) using Kieselgel 60F-254-0.25 mm plates. The ratio-to-front (Rf) is the ratio between the migration distance of a compound on a given support and the migration distance of an eluent.
The figures below describe the preparation of gem-difluorinated glycoconjugate compounds having the formula:
Preparation of Initial Lactone 1
Initially, a lactone 1 is prepared by benzylation of methylgalactopyrannoside 2 ( FIG. 1 ), deprotection of the anomeric position ( FIG. 2 ), followed by oxidation ( FIG. 3 ):
In a flask under an inert atmosphere containing methyl-D-galactopyranoside 2 (5 g; 26 mmol; 1 eq.) and tetrabutylammonium iodide nBu 4 NI (500 mg; 1.3 mmol; 0.05 eq.) in dimethylformaldehyde DMF (250 ml), the addition is made of sodium hydride NaH (3.7 g; 0.15 mol; 6 eq.) in small portions. Then benzyl bromide BnBr (18 ml; 0.15 mol; 6 eq.) is added and the mixture is left under stirring for at least 36 hours.
The medium is hydrolysed with water. The aqueous phase is then extracted three times with ether. The organic phases are then collected, washed several times in water, dried over magnesium sulphate, filtered and then evaporated.
The product obtained is purified by chromatography on a column of silica eluting with a cyclohexane/ethyl acetate mixture in a proportion of nine to one. After concentrating the collected fractions, the product 3 is in the form of a white crystals with a weight yield of 95%.
Characterisation of Product 3:
Rf: 0.38 (cyclohexane/ethyl acetate 8/2).
C 35 H 38 O 6 M=554.67 g.mol −1
In a flask containing 1-O-Methyl-2,3,4,6-Tetra-O-Benzyl-D-galactopyranose 3 (5.5 g; 9.92 mmol) in 80 mL acetic acid 4, 11 mL sulphuric acid H 2 SO 4 are added at a molar concentration of 3M. The reaction medium is heated to 100° C. for one hour. The solution is then diluted in 100 mL cold water.
The mixture is extracted four times with 100 mL toluene. The organic phases are collected, then washed with 100 mL of a saturated solution of sodium hydrogenocarbonate NaHCO 3 and finally with 100 mL water. The organic phase is then dried over magnesium sulphate, filtered and concentrated.
The product obtained is purified by silica column chromatography eluting with a cyclohexane/ethyl acetate mixture in the proportion of 8.5 to 1.5. After concentrating the collected fractions, the product 5 is in the form of white crystals with a weight yield of 75%.
Characterization of Product 5:
Rf: 0.65 (cyclohexane/ethyl acetate 6/4). C 34 H 36 O 6 M=540.65 g.mol −1
In a flask under an inert atmosphere containing 2,3,4,6-Tetra-O-Benzyl-D-Galactopyranose 5 (4 g; 7.4 mmol) the addition is made of dimethylsulphoxide DMSO (25.6 mL) and acetic anhydride Ac 2 O (16.8 mL). The mixture is left under stirring for 12 hours.
A saturated solution of sodium hydrogenocarbonate NaHCO 3 is added, then the aqueous phase is extracted four times with ether. The organic phases are collected then washed five times with water. This organic phase is then dried over magnesium sulphate, filtered and concentrated.
The product is then purified on a silica chromatographic column using as eluent a cyclohexane/ethyl acetate mixture in a proportion of eight to two. After concentrating the collected fractions, the lactone 1 is in the form of a colourless oil with a weight yield of 82%.
Characterization of Product 1:
Rf: 0.61 (cyclohexane/ethyl acetate 8/2). C 34 H 34 O 6 M=538.63 g.mol −1
NMR 1 H (CDCl 3 , 300 MHz)
3.6 (m, 2H, H 6 ); 3.8 (dd, 2.1-9.6, 1H, H 3 ); 4.1 (s, 1H, H 4 ); 4.2 (m, 1H, H 5 ); 4.4-5.1 (m, 9H, H 2 ; 4OC H 2 Bn); 7.2 (m, 20H, H ar.)
NMR 13 C (CDCl 3 , 75.5 MHz)
67.4 (C 6 ); 72.4 (C 5 ); 72.6 (O C H 2 Bn); 73.5 (O C H 2 Bn); 74.5 (C 4 ); 75.1 (O C H 2 Bn); 77.1 (C 2 ); 79.9 (C 3 ); 127.4-128.3 ( C ar.); 137.2; 137.3; 137.6 ( C ar. quat.); 169.8 ( C O).
Preparation of a Gem Difluoroester Compound 7
The addition of a bromodifluoroester to the lactone 1 is made using a Reformatsky reaction ( FIG. 4 ).
In a flask, under an inert atmosphere, containing zinc Zn (1.7 g; 26 mmol; 7 eq.) previously activated and scoured, the addition is made of tetrahydrofurane THF (30 mL). The medium is placed under a reflux, then a mixture consisting of lactone 1 (2 g; 3.7 mmol; 1 eq.) and ethyl bromodifluoroacetate 6 (1.42 mL; 11 mmol; 3 eq.) in the THF (30 mL) is added dropwise. The reaction is left under the reflux for 3 hours. On return to ambient temperature, the zinc is filtered; a 1N solution of hydrochloric acid HCl (60 mL) then dichloromethane (6 mL) are added to the reaction medium.
The aqueous and organic phases are separated and the aqueous phase is again extracted two times with dichloromethane. The organic phases are collected, dried over magnesium sulphate, filtered and then concentrated.
The product is subsequently purified on a silica chromatographic column eluting with a cyclohexane/ethyl acetate mixture in a proportion of eight to two. After concentrating the collected fractions, the product 7 is in the form of white crystals with a weight yield of 82%.
Characterization of Product 7:
Rf: 0.35 (cyclohexane/ethyl acetate 8/2). C 38 H 40 F 2 O 8 M=662.72 g.mol −1
NMR 19 F (CDCl 3 ; 282.5 MHz)
−118.4 (d, J F-F =256 Hz); −120.2 (d, J F-F =256 Hz).
NMR 1 H (CDCl 3 , 300 MHz)
1.1 (t, 7.2, 3H, C H 3 ); 3.4-3.5 (m, 2H, H 6 ); 3.7-3.8 (dd, 2.5-9.5, 1H, H 3 ); 3.8 (d, 2, 1H, H 4 ); 4-4.1 (m, 3H, H 5 ; C H 2 ); 4.25-4.85 (m, 9H, H 2 ; 4OC H 2 Bn); 7.2 (m, 20H, H ar).
NMR 13 C (CDCl 3 , 75.5 MHz)
14.2 ( C H 3 ); 63.6 ( C H 2 ); 68.6 (C 6 ); 71.7 (C 5 ); 73.2 (O C H 2 Bn); 73.9 (O C H 2 Bn); 74.1 (C 4 ); 74.9 (O C H 2 Bn); 75.1 (C 2 );75.8 (O C H 2 Bn); 81.2 (C 3 ); 96.9 (t, 27 Hz, C 1 ); 113 (t, 264 Hz, C F 2 ); 128.0-128.9 ( C ar.); 138.2; 138.3; 138.6; 139.1 ( C ar. quat.); 163.3 (t, 31 Hz, C O 2 Et).
First Access Route For Adding the Peptide Chain:
The addition of the peptide chain may be performed in two different ways. The first was used for the synthesis of a Lysine-Alanine-Alanine monomer. Firstly the first amino acid is added which reacts with the difluoroester function ( FIG. 5 ). After obtaining the first glycoaminoacid, the ester of the lysine is saponified ( FIG. 6 ), then the Alanine-Alanine unit is added via peptide coupling ( FIG. 7 ).
The N then O terminal functions of the monomer so obtained are then deprotected ( FIGS. 8 and 9 ), and finally debenzylation of the galactoside unit is performed ( FIG. 10 ):
A) Addition of the First Aminoacid ( FIG. 5 ):
In a flask, under an inert atmosphere, containing starting product 7 (50 mg; 0.075 mmol; 1 eq.) in solution and the acetate of Boc-lysine-OMe 8 (48 mg; 0.15 mmol; 2 eq.) in dichloroethane (3 mL), the addition is made of triethylamine Et 3 N (53 μl; 0.375 mmol; 5 eq.). The mixture is heated under a reflux for 48 hours then hydrolysed with water and extracted three times in dichloromethane. The organic phases are collected, dried over magnesium sulphate, filtered and then concentrated.
The solvent is evaporated then the mixture is purified by chromatography on a silica column using as eluent a cyclohexane/ethyl acetate mixture in the proportion of seven to three. After concentrating the collected fractions, the product 9 is in the form of a white solid with a weight yield of 84%.
Characterization of Product 9:
Rf: 0.58 (cyclohexane/ethyl acetate 7/3). C 48 H 58 F 2 N 2 O 11 M=876.98 g.mol −1
NMR 19 F (CDCl 3 , 282.5 MHz)
−117.1 (d, J F-F =260 Hz); −121.8 (d, J F-F =260 Hz).
NMR 1 H (CDCl 3 , 300 MHz)
1.1 (m, 2H, C H 2 );1.2-1.5 (m, 2H, C H 2 );1.3 (s, 9H, (C H 3 ) 3 C);1.6 (m, 2H, C H 2 ); 3.0-3.1 (m, 2H, C H 2 NH); 3.4-3.5 (m, 2H, H 6 ); 3.6 (s, 3H, OC H 3 ); 3.8 (m, 2H, H 3 ; H 4 ); 4.1 (m, 2H, C H NH (Lys); H 5 ); 4.2-4.9 (m, 8H, 4OC H 2 Bn); 4.3 (d, 3.3, 1H, H 2 ); 5 (s, 2H, 2N H ); 6.7 (s, 1H, 1N H ); 7.2 (m, 20H, H ar.).
NMR 13 C (CDCl 3 , 75.5 MHz)
22.9 ( C H 2 ); 27.3 ( C H 2 ); 28.7 (( C H 3 ) 3 C); 32.4 ( C H 2 ); 39.4 ( C H 2 N); 52.7 (O C H 3 ); 53.6 (N C H Lys); 68.7 (C 6 ); 71.1 (C 5 ); 73.4 and 73.7 (20 C H 2 Bn); 74.5 (C 4 ); 75.0 (O C H 2 Bn; C 2 ); 75.8 (O C H 2 Bn); 80.3 ((CH 3 ) 3 C ); 80.9 (C 3 ); 97.1 (t, 28 Hz, C 1 );112.8 (t; 260 Hz); 128.0-128.9 ( C ar.); 138.2; 138.3; 138.7; 139.0 ( C ar. quat.); 155.9 ( C O(Boc)); 164.1 (t, 28 Hz, CF 2 C ONH); 173.6 ( C O 2 Et).
B) Saponification of the Lysine Ester ( FIG. 6 ):
In a flask containing starting product 9 (1.25 g; 1.43 mmol; 1 eq.) in THF (10 mL), the addition is made of lithine LiOH (70 mg; 2.9 mmol; 2 eq.) in solution in water (1 mL) and the mixture is left to react for 24 hours. The reaction medium is then collected in dichloromethane. A 1N solution of hydrochloric acid HCl (5 mL) is added. The aqueous phase is extracted three times in dichloromethane. The organic phases are collected, washed in water (5 mL), dried over magnesium sulphate, filtered and then concentrated. The product 10 obtained is in the form of a white solid with quantitative weight yield.
Characterization of Product 10:
C 47 H 56 F 2 N 2 O 11 M=862.95 g.mol −1
NMR 19 F (CDCl 3 , 282,5 MHz)
−117.2 (d, J F-F =260 Hz); −121.5 (d, J F-F =260 Hz).
NMR 1 H (CDCl 3 , 300 MHz)
1.2 (m, 2H, C H 2 ); 1.3-1.5 (m, 2H, C H 2 ); 1.3 (s, 9H, (C H 3 ) 3 C); 1.6 (m, 2H, C H 2 ); 3.0-3.1 (m, 2H, C H 2 NH); 3.4-3.5 (m, 2H, H 6 ); 3.8 (m, 2H, H 3 ; H 4 ); 4.1 (m, 2H, C H NH (Lys); H 5 ); 4.2-4.9 (m, 8H, 4OC H 2 Bn); 4.4 (d, 3.4, 1H, H 2 ); 5.1 (d, 7.5, 1H, N H ); 6.6 (s, 1H, N H ); 7.2 (m, 20H, H ar.).
NMR 13 C (CDCl 3 , 75.5 MHz) 22.6 ( C H 2 ); 27.3 ( C H 2 ); 28.7 (( C H 3 ) 3 C); 32.0 ( C H 2 ); 39.4 ( C H 2 N); 53.7 (N C H Lys); 68.7 (C 6 ); 71.1 (C 5 ); 73.4 et 73.7 (2O C H 2 Bn); 74.4 (C 4 ); 74.9 (C 2 ); 75.0 (O C H 2 Bn); 75.8 (O C H 2 Bn); 80.5 ((CH 3 ) 3 C ); 80.9 (C 3 ); 97.0 (t, 28 Hz, C 1 ); 112.8 (t; 260 Hz); 127.9-128.9 ( C ar.); 138.1; 138.2; 138.6; 139.0 ( C ar. quat.); 156.2 ( C O(Boc)); 164.0 (t, 28 Hz, CF 2 C ONH); 176.7 ( C O 2 H).
C) Addition of an Alanine-Alanine Unit By Peptide Coupling ( FIG. 7 ):
In a flask under an inert atmosphere containing acid 10 (520 mg; 0.6 mmol; 1 eq.) in dichloromethane (15 mL), the addition is made of carbonyldiimadozale CDI (117 mg; 0.72 mmol; 1.2 eq.). The mixture is left under stirring for one hour. Then a solution prepared under an inert atmosphere and consisting, of trifluoroacetate-Alanine-Alanine-OMe 11 (229 mg; 0.79 mmol; 1.3 eq.), of diisopropylethylamine DIEA (347 μL; 1.99 mmol; 3.3 eq.) in dichloromethane (15 mL) is added to this mixture and the reaction medium is left under stirring for 36 hours. The mixture is then hydrolysed with water, followed by extraction three times in dichloromethane. The organic phases are collected, dried over magnesium sulphate, filtered and then concentrated.
The solvent is evaporated then the mixture is purified by chromatography on a silica column using as eluent a cyclohexane/ethyl acetate mixture in a proportion of three to seven. After concentrating the collected fractions, the product 12 is in the form of a white solid with a weight yield of 55%.
Characterization of Product 12:
Rf: 0.46 (ethyl acetate). C 54 H 68 F 2 N 4 O 13 M=1019.13 g.mol −1
NMR 19 F (CDCl 3 , 282.5 MHz)
−116.9 (d, J F-F =260 Hz); −121.7 (d, J F-F =260 Hz).
NMR 1 H (CDCl 3 , 300 MHz)
1.2-1.4 (m, 10H, 2C H 3 ; 2C H 2 ); 1.3 (s, 9H, (C H 3 ) 3 C); 1.6 (m, 2H, C H 2 ); 3.0-3.2 (m, 2H, NHC H 2 ); 3.4-3.5 (m, 2H, H 6 ); 3.6 (s, 3H, OC H 3 ); 3.8-3.9 (m, 2H, H 3 ; H 4 ); 4.0 (m, 1H, C H NH (Lys)); 4.1 (t, 6.2, 1H, H 5 ); 4.2-4.9 (m, 10H, 4OC H 2 Bn; 2C H (Ala)); 4.3 (d, .,3, 1H, H 2 ); 5.3 (d, 6.4, 2H, 2N H ); 7 (m, 1H, N H ); 7.2 (m, 20H, H ar.).
NMR 13 C (CDCl 3 , 75.5 MHz)
18.3 and 18.6 (2 C H 3 ); 22.8 ( C H 2 ); 28.7 (( C H 3 ) 3 C and C H 2 ); 32.1 ( C H 2 ); 39.3 ( C H 2 N); 48.5 and 49.2 (2 C H Ala); 52.9 (O C H 3 ); 54.8 (N C H Lys); 68.7 (C 6 ); 71.1 (C 5 ); 73.5 and 73.7 (2O C H 2 Bn); 74.5 (C 4 ); 75.0 (O C H 2 Bn; C 2 ); 75.7 (O C H 2 Bn); 80.5 ((CH 3 ) 3 C ); 80.8 (C 3 ); 97.1 (t, 27 Hz, C 1 );127.9-128.9 ( C ar.); 138.2;138.3;138.7; 139.0 ( C ar. quat.); 156.0 ( C O(Boc));164.2 (t, 28 Hz, CF 2 C ONH); 172.3 and 172.5 (2 C ONH); 173.6 ( C O 2 Et).
D) Deprotection of the N Then O Terminal Functions of the Monomer Obtained ( FIGS. 8 and 9 ):
In a flask under an inert atmosphere containing starting product 12 (0.607 mg; 0.6 mmol; 1 eq.) in dichloromethane (10 mL) the addition is made of trifluoroacetic acid TFA (900 μL; 12 mmol; 20 eq.). The mixture is left to react for 12 hours then the reaction medium is concentrated. Four to five co-evaporations with toluene are conducted to obtain product 13 in the form of a colourless oil with quantitative yield.
Characterization of Product 13:
C 51 H 61 F 5 N 4 O 13 M=1033.04 g.mol −1
NMR 19 F (CDCl 3 , 282.5 MHz)
−75.9; −116.9 (d, J F-F =260 Hz); −120.7 (d, J F-F =260 Hz).
NMR 1 H (CDCl 3 , 300 MHz)
1.2-1.4 (m, 10H, 2C H 3 ; 2C H 2 ); 1.6 (m, 2H, C H 2 ); 3.0 (m, 2H, NHC H 2 ); 3.4 (m, 2H, H 6 ); 3.5 (s, 3H, OC H 3 ); 3.8-3.9 (m, 3H, C H NH (Lys);H 3 ; H 4 ); 4.1 (m, 1H, H 5 ); 4.2-4.9 (m, 11H, 4OC H 2 Bn; 2C H (Ala); H 2 ); 7.2 (m, 20H, H ar.).
NMR 13 C (CDCl 3 , 75.5 MHz)
17.7 et 18.1 (2 C H 3 ); 21.9 ( C H 2 ); 28.5 ( C H 2 ); 31.0 ( C H 2 ); 39.1 ( C H 2 N); 48.7 and 50.0 (2 C H Ala); 52.8 (O C H 3 ); 53.7 (N C H Lys); 68.8 (C 6 ); 71.2 (C 5 ); 73.3 and 73.8 (2O C H 2 Bn); 74.3 (C 4 ); 75.0 (O C H 2 Bn); 75.1 (C 2 ); 75.8 (O C H 2 Bn); 80.9 (C 3 ); 97.1 (t, 27 Hz, C 1 );127.9-128.9 ( C ar.); 138.1; 138.3; 138.6; 138.9 ( C ar. quat.); 162.0 (qdt, 34 Hz, C OCF 3 );164.2 (t, 28 Hz, CF 2 C ONH); 169.4 and 172.7 (2 C ONH); 173.6 ( C O 2 Et).
In a flask containing starting product 13 (671 mg; 0.65 mmol; 1 eq.) in THF (5 mL) the addition is made of lithine LiOH (47 mg; 1.9 mmol; 3 eq.) in solution in water (1 mL). The mixture is left to react 12 hours then collected in the dichloromethane. A 1N solution of hydrochloric acid HCl (4 mL) is added and the aqueous phase is extracted three times with dichloromethane. The organic phases are collected, washed in water (4 mL) then concentrated.
Four to five co-evaporations with toluene are conducted to remove traces of water and obtain product 14 in the form of a white solid with quantitative yield.
Characterization of Product 14:
C 48 H 59 ClF 2 N 4 O H M= 941.45 g.mol −1
NMR 19 F (CD 3 OD, 282.5 MHz)
−120.4; −120.5.
NMR 1 H (CD 3 OD, 300 MHz)
1.2-1.3 (m,12H, 2C H 3 ; 2C H 2 ); 1.6 (m,2H, C H 2 ); 3.0 (m, 2H, NHC H 2 ); 3.1 (m,2H, H 6 ); 3.5 (m, 3H, C H NH (Lys);H 3 ; H 4 ); 3.8-3.9 (m, 1H, H 5 ); 4.2-4.9 (m,11H, 4C H 2 OBn; 2C H (Ala); H 2 ); 7.2 (m, 20H, H ar.).
NMR 13 C (CD 3 OD, 75.5 MHz)
17.7 and 18.1 (2 C H 3 ); 23.5 ( C H 2 ); 29.9 ( C H 2 ); 32.7 ( C H 2 ); 40.5 ( C H 2 N); 49.7 and 50.0 (2 C H Ala); 53.7 (N C H Lys); 70.2 (C 6 ); 72.4 (C 5 ); 74.2 and 74.7 (2O C H 2 Bn); 76.1 and 76.6 (2O C H 2 Bn); 76.7 (C 4 and C 2 ); 82.1 (C 3 ); 98.0 (t, 27 Hz, C 1 ) 111.7 (t, 260 Hz; C F 2 ); 129-130.6 ( C ar.); 139.7;140.1; 140.2; 140.5 ( C ar. quat.); 165.5 (t, 28 Hz, CF 2 C ONH); 174.0 and 174.5 ( C O).
E) Debenzylation of the Galactoside Unit ( FIG. 10 ):
A flask containing starting product 14 (150 mg; 0.16 mmol) in a mixture of acetic acid CH 3 CO 2 H (5 mL), tetrahydrofurane THF (1.5 mL) and water (1.5 mL) in the presence of a spatula tip of palladium on charcoal Pd/C is placed under a hydrogen atmosphere. The i mixture left under stirring overnight then filtered through a Millipore® filter. The mixture is then concentrated to obtain product 15 in the form of a white solid with a yield of 70%.
Characterization of Product 15:
C 20 H 35 ClF 2 N 4 O 11 M=580.96 g.mol −1
NMR 19 F (CD 3 OD, 282.5 MHz)
−120.0 (d, J F-F =258 Hz); −121.3 (d, J F-F =258 Hz); −121.6 (d, J F-F =258 Hz); −123.0 (d, J F-F =258 Hz),
NMR 1 H (CD 3 OD, 300 MHz) 1.4 (2d, 7.7, 6H, 2C H 3 );1.3-1.5 (m, 2H, C H 2 ); 1.7 (m, 2H, C H 2 ); 1.9 (m, 2H, C H 2 ); 3.2 (m, 2H, NHC H 2 ); 3.7-3.8 (m, 4H, H 6 ; H 5 ; H 3 ); 4.2 and 4.4 (2m, 2H, H 2 );3.9 (m, 1H, C H NH (Lys)); 4.3 and 4.5 (2m, 2H, 2C H (Ala)).
NMR 13 C (CD 3 OD, 75.5 MHz)
18.7 and 18.9 (2 C H 3 ); 23.5 ( C H 2 ); 30.1 ( C H 2 ); 32.8 ( C H 2 ); 40.5 ( C H 2 N); 50.9 (2 C H Ala); 54.7 (N C H Lys); 64.7 (C 6 ); 72.7(C 5 ), 76.2, 77.7 (C 4 et C 2 ), 82.4 (C 3 ); 100.6 (C 1 ); 115.6 (t, 260 Hz; C F 2 ); 165.5 (CF 2 C ONH); 170.7 and 174.6 ( C O).
Mass (FAB+): 545 (M + −Cl)
Second Access Route for the Preparation of the Peptide Chain:
This consists of the saponification of the gem-difluoroester derivative 7 which will subsequently be coupled with different peptides.
A) Saponification of the Gem-Difluoroester Derivative 7 ( FIG. 11 )
In a flask containing the ester 7 (0.5 g;1.75 mmol, 1 eq.) in THF (5 mL), the addition is made of an aqueous solution of lithine LiOH (84 mg; 3.5 mmol, 2 eq.) solubilised in a minimum amount of water. The mixture is left under stirring for twelve hours then collected with ethyl acetate. The mixture is acidified with an aqueous 1N solution of hydrochloric acid then extracted several times with ethyl acetate. The organic phases are collected, dried over MgSO 4 , filtered and concentrated.
Product 16 is obtained in the form of a white oil with quantitative yield.
Characterization of Product 16:
C 36 H 36 F 2 O 8 M=634.66 g.mol −1
NMR 19 F (CDCl 3 , 282.5 MHz)
−117.3 (d, J F-F =259 Hz); −119.0 (d, J F-F =259 Hz).
NMR 1 H (CDCl 3 , 300 MHz) 3.2 (dd, 4.5 Hz and 9.8 Hz,1H, H 6 ); 3.5 (dd, 7.7 Hz and 9.8 Hz,1H, H 6 ); 3.7 (d, 2 Hz, 1H, H 4 ); 3.8 (dd, 2.6 Hz and 9.5 Hz, 1H, H 3 ); 4 (dd, 4.5 Hz and 7.7 Hz;1H, H 5 ); 4.3-4.9 (m, 9H, H 2 ; 4OC H 2 Bn); 7.2 (m, 20H, H ar).
NMR 13 C (CDCl 3 , 75.5 MHz)
69.4 (C 6 ); 71.7 (C 5 ); 73.5 (O C H 2 Bn); 74.0 (O C H 2 Bn); 74.1 (C 4 ); 75.0 (O C H 2 Bn); 75.1 (C 2 );75.9 (O C H 2 Bn); 80.8 (C 3 ); 95.4 (t, 27 Hz, C 1 ); 112.5 (t, 260 Hz, C F 2 ); 127.8-129.0 ( C ar.); 137.6;138.0; 138.1 ( C ar. quat.); 163.1 (t, 30 Hz, C O 2 H).
B) Preparation of the Different Peptides to be Coupled With the Gem-Difluorinated Compound 16.
Each of the peptides to be coupled with the gem-difluorinated compound 16 is prepared using a series of deprotection reactions and peptide coupling:
A first coupling between two alanines is performed ( FIG. 12 ):
In a flask under an inert atmosphere containing Boc-Alanine-OH 17 (1 g; 5.29 mmol; 1 eq.) in dichloromethane (25 mL), the addition is made of carbonyldiimadozale CDI (882 mg; 5.44 mmol; 1.03 eq.). The mixture is left under stirring for one hour. To this mixture is added a solution prepared under an inert atmosphere and consisting of Cl −+ H 3 N-Alanine-OMe 18 (738 mg; 5.29 mmol; 1 eq.), and diisopropylethylamine DIEA (1.94 mL; 11.1 mmol; 2.1 eq.) in dichloromethane (15 mL). The mixture is left under stirring for 36 hours then the medium is hydrolysed with water and extracted three times with dichloromethane. The organic phases are collected, dried over magnesium sulphate, filtered and then concentrated.
The solvent is evaporated then the mixture is purified by chromatography on a silica column using as eluent a cyclohexane/ethyl acetate mixture in a proportion of five to five. After concentrating the collected fractions, product 19 is in the form of a white solid with a weight yield of 82%.
Characterization of Product 19:
C 12 H 22 N 2 O 5 M=274.31 g.mol −1
NMR 1 H (CDCl 3 , 300 MHz)
1.3 (2d, 7.2, 6H, 2C H 3 ); 1.4 (s, 9H, (( C H 3 ) 3 C); 3.7 (s, 3H, OC H 3 ); 4.2 (m, 1H, C H ); 4.6 (m, 1H, C H ); 5.2 (d, 7.4, 1H, N H ); 6.9 (s, 1H, N H ).
NMR 13 C (CDCl 3 , 75.5 MHz)
18.6 and 18.8 (2 C H 3 ); 28.7 (( C H 3 ) 3 C); 48.3 and 50.2 (2 C H); 52.8 (O C H 3 ); 80.4 ((CH 3 ) 3 C ); 155.8 0 ( C O(Boc)); 172.8 and 173.6 ( C ONH and C O 2 Et).
The O-terminal function of the dipeptide 19 obtained is deprotected, then dipeptide 19 is coupled with an N-protected lysine aminoacid ( FIG. 13 ):
1) Deprotection of the Dipeptide Unit
In a flask under an inert atmosphere containing Boc-Alanine-Alanine-OMe 19 (1 g; 3.8 mmol; 1 eq.) in dichloromethane (20 mL), the addition is made of trifluoroacetic acid TFA (5.6 mL; 76 mmol; 20 eq.). Four to five co-evaporations with toluene are performed.
2) Peptide Synthesis
In a flask under an inert atmosphere containing Boc-Lysine(Z)-OH 20 (1.32 g; 3.46 mmol; 1 eq.) in dichloromethane (20 mL), the addition is made of carbonyldiimadozale CDI (560 mg; 3.56 mmol; 1.03 eq.). The mixture is left under stirring for one hour. Then to this product a solution is added prepared under an inert atmosphere and consisting of CF 3 CO 2 −+ H 3 N-Alanine-Alanine-OMe obtained during the previous reaction (3.8 mmol; 1.1 eq.), and of diisopropylethylamine DIEA (1.26 mL; 7.27 mmol; 2.1 eq.) in dichloromethane (20 mL). The mixture is left under stirring for 36 hours then hydrolysed with water and extracted three times with dichloromethane. The organic phases are collected, dried over magnesium sulphate, filtered and then concentrated.
The solvent is evaporated then the mixture is purified by chromatography on a silica column using ethyl acetate as eluent. After concentrating the collected fractions, product 21 is in the form of a white solid with a weight yield of 66%.
Characterization of Product 21:
C 26 H 40 N 4 O 8 M=536.62 g.mol −1
NMR 1 H (CDCl 3 , 300 MHz)
1.3 (d, 7.2, 6H, 2C H 3 ); 1.4 (s, 9H, (( C H 3 ) 3 C) 1.3-1.7(m 6H;3C H 2 ); 3.1 (m, 2H, NHC H 2 ); 3.7 (s, 3H, OC H 3 ); 4.1 (m, 1H, C H Lys); 4.6 (m, 2H, C H Ala); 5.0 (s, 2H, PhC H 2 ); 5.6 and 5.7 (m, 2H, 2N H ); 7.3 (m, 5H, H ar.); 7.4 (d, 7Hz,14Hz, 1H, N H ).
NMR 13 C (CDCl 3 , 75.5 MHz)
18.1 and 18.7 (2 C H 3 ); 22.7 ( C H 2 ); 28.7 (( C H 3 ) 3 C); 29.7 ( C H 2 ); 32.5 ( C H 2 ); 40.7 (N C H 2 ); 48.4 and 49.1 (2 C H);52.7 (O C H 3 ); 54.6 ( C H Lys); 66.8 (O C H 2 Bn); 80.2 ((CH 3 ) 3 C ); 128.3-128.8 ( C ar.); 137.1 ( C ar. quat.); 156.2 and 157.1 ( C O(Boc) and C O(Z)); 172.4, 172.7 and 173.6 (2 C ONH and C O 2 Et).
The amino function positioned on the side chain of compound 21 is deprotected by hydrogenation ( FIG. 14 ). Compound 22 obtained may then be directly involved in peptide coupling with product 16 to lead to previously described compound 12 via another synthesis route described below under paragraph C).
A flask containing starting product 21 (1.6 g; 3 mmol) in methanol (20 mL) in the presence of a spatula tip of palladium on charcoal Pd/C is placed under a hydrogen atmosphere. The mixture is left under stirring overnight then filtered through a Millipore filter. The medium is then concentrated. Product 22 is in the form of a white powder with quantitative yield.
Characterization of Product 22:
C 18 H 34 N 4 O 6 M=402.49 g.mol −1
RMN 1 H (CD 3 OD, 300 MHz)
1.4 (2d, 7.2 Hz, 6H, 2C H 3 ); 1.5 (s, 9H, (( C H 3 ) 3 C) 1.5-1.8 (m 6H;3C H 2 ); 2.7 (m, 2H, NHC H 2 ); 3.7 (s, 3H, OC H 3 ); 4 (m, 1H, C H Lys); 4,4 (m, 2H, C H Ala).
Tripeptide units are deprotected at their N-terminal function ( FIG. 15 ) or O-terminal function ( FIG. 15 ) and peptide synthesis between tripeptide units deprotected at their N-terminal function and tripeptide units deprotected at their O-terminal function is performed. ( FIG. 15 ):
N-deprotection ( FIG. 15 )
In a flask under an inert atmosphere containing Boc-Lysine(Z)-Alanine-Alanine-OMe 21 (2 g ; 3.7 mmol ; 1 eq.) in dichloromethane (40 mL), the addition is made of trifluoroacetic acid TFA (5.5 mL ; 75 mmol ; 20 eq.). The mixture is left to react for 12 hours then concentrated. Four to five co-evaporations with toluene are conducted to obtain CF 3 CO 2 −+ H 3 N-Lysine(Z)-Alanine-Alanine-OMe 23.
O-deprotection ( FIG. 15 )
In a flask containing Boc-Lysine(Z)-Alanine-Alanine-OMe 21 (2 g ; 3.7 mmol ; 1 eq.) in ethanol (45 mL), the addition is made of lithine LiOH (107 mg ; 4.5 mmol ; 1.2 eq.) in solution in water (2 mL). The mixture is left to react 12 hours. The reaction medium is afterwards evaporated, then collected with the dichloromethane. An aqueous 1N solution of hydrochloric acid HCl (20 mL) is added. The aqueous phase is extracted three times with dichloromethane. The organic phases are collected, dried over magnesium sulphate, filtered then concentrated to obtain Boc-Lys(Z)-Ala-Ala-OH 24 .
Peptide synthesis ( FIG. 15 )
In a flask under an inert atmosphere containing Boc-Lysine(Z)-Alanine-Alanine-OH 24 (3.7 mmol ; 1 eq.) in dichloromethane (50 mL), the addition is made of carbonyldiimadozale CDI (665 mg ; 4.10 mmol ; 1.1 eq.). The mixture is left under stirring for one hour. Then, to this product is added a solution prepared under an inert atmosphere and consisting of CF 3 CO 2 −+ H 3 N-Lysine(Z)-Alanine-Alanine-Ome 23 (3.7 mmol ; 1 eq.), and diisopropylethylamine DIEA (1.62 mL ; 9.32 mmol ; 2.5 eq.) in the dichloromethane (50 mL). The mixture is left under stirring for 48 hours. The medium is hydrolysed with water, then extracted two times with dichloromethane and two times with chloroform. The organic phases are collected, dried over magnesium sulphate, filtered then concentrated.
The solvent is evaporated and the mixture is purified by chromatography on a silica column eluting with an ethyl/methanol mixture in a proportion of nine to one. After concentrating the collected fractions, product 25 is in the form of a white powder with a weight yield of 56%.
Characterization of Product 25:
C 46 H 68 N 8 O 13 M=941.08 g.mol −1
NMR 1 H (DMSO,300 MHz)
1.3 (m, 12H, 4C H 3 ); 1.4 (s, 9H, (( C H 3 ) 3 C) 1.3-1.7(m 12H;6C H 2 ); 3.0 (m, 4H, 2NHC H 2 ); 3.6 (s, 3H, OC H 3 ); 4.1 (m, 1H, C H Lys); 4.3 (m, 5H, 5C H Ala et Lys); 5.0 (s, 4H, PhC H 2 ); 5.0 (s, 2H, PhC H 2 ); 6.9 (m, 1H, N H ); 7.3 (m, 5H, H ar.).
NMR 13 C (DMSO,75.5 MHz)
17.2, 18.3, 18.4 and 18.6 (4 C H 3 ); 22.8 and 23.2 (2 C H 2 ); 28.5 (( C H 3 )3C); 29.3 and 29.5 (2 C H 2 ); 31.8 and 32.0 (2 C H 2 ); 39.5 and 39.8 (2N C H 2 ); 47.8, 43.0, 48.2 and 48.5 (4 C H Ala); 52.2 (O C H 3 ); 52.6 and 54.6 (2 C H Lys); 65.4 (2O C H 2 Bn); 78.4 ((CH 3 ) 3 C ); 128.0 and 128.6 ( C ar.); 137.6 ( C ar. quat.); 155.7 and 156.4 ( C O(Boc) and 2 C O(Z)); 171.3, 172.3, 172.4, 172.5 and 173.3 (6 C ONH and C O 2 Et).
The amino function positioned on the side chain of compound 24 is deprotected by hydrogenation ( FIG. 16 ):
A flask containing starting product 25 (400 mg; 0.43 mmol) in methanol (10 mL) in the presence of a spatula tip of palladium on charcoal Pd/C is placed under a hydrogen atmosphere. The mixture is left under stirring overnight, filtered through a Millipore® filter. The medium is then concentrated. Product 26 is in the form of a white powder with quantitative yield.
Characterization of Product 26:
C 30 H 56 N 8 O 9 M=672.81 g.mol −1
NMR 1 H (DMSO, 300 MHz)
1.2 (m, 12H, 4C H 3 ); 1.4 (s, 9H, (( C H 3 ) 3 C) 1.3-1.7(m 12H;6C H 2 ); 2.6 (m, 4H, 2NHC H 2 ); 3.6 (s, 3H, OC H 3 ); 3.8 (m, 1H, C H Lys); 4.2 (m, 5H, 5C H Ala and Lys).
Mass (ES+): 696 (M+Na); 674 (M+H)
C) Coupling of the Gem-Difluorinated Compound 16 With Peptide 22 ( FIG. 17 )
In a flask under an inert atmosphere containing acid 16 (2 g; 3.15 mmol; 1.05 eq.), peptide 22 (1.2 g; 3.0 mmol; 1 eq.), 1-hydroxybenzotriazole HOBT (425 mg; 3.15 mmol; 1.05 eq.) and N-methylmorpholine NMM (346 μL; 3.15 mmol; 1.05 eq.) in DMF (50 mL), the addition is made of EDCI (604 mg; 3.15 mmol; 1.05 eq.). The reaction medium is left under stirring for 48 hours then the solvent is evaporated and the medium collected in a water-dichloromethane mixture. The aqueous phase is extracted three times with dichloromethane. The organic phases are collected, dried on MgSO 4 , filtered and concentrated.
Product 12 is obtained with a yield of 58%. This product has already been previously characterized.
D) Coupling of the Gem-Difluorinated Compound 16 With Peptide 26 ( FIG. 17 )
In a flask under an inert atmosphere containing acid 16 (200 mg; 0.32 mmol; 1 eq.), peptide 26 (105 mg; 0.16 mmol; 0.5 eq.), 1-hydroxybenzotriazole HOBT (45 mg; 0.33 mmol; 1.05 eq.) and N-methylmorpholine NMM (32 μL; 0.33 mmol; 1.05 eq.) in DMF (3 mL), the addition is made of EDCI (63 mg; 0.33 mmol; 1.05 eq.). The reaction medium is left under stirring for 48 hours then concentrated. To the medium is added a water-dichloromethane mixture. The aqueous phase is extracted three times with dichloromethane. The organic phases are collected, dried over MgSO 4 , filtered and concentrated.
Product 27 is obtained in the form of a white powder with a yield of 35%.
Characterization of Product 27:
C 102 H 124 F 4 N 8 O 23 M=1906.11 g.mol −1
19 F NMR (CDCl 3 , 282.5 MHz)
−120.4.
1 H NMR (CD 3 OD, 300 MHz)
1.2 (m, 12H, 4C H 3 ); 1.3 (s, 9H, (C H 3 ) 3 C); 1.3-1.7 (m, 12H, 6C H 2 ); 3.0 (m, 4H, 2NHC H 2 ); 3.4 (m, 4H, H 6 ); 3.6 (s, 3H, OC H 3 ); 3.8 (m, 1H, C H NH (Lys)); 3.9 (m, 4H, H 3 ; H 4 ); 4.0 (m, 2H, H 5 ); 4.1-4.8 (m, 23H, 8OC H 2 Bn, 4C H (Ala), C H NH (Lys), 2H 2 ); 7.2 (m, 40H, H ar.).
13 C NMR (CD 3 OD, 75.5 MHz)
16.1, 16.2, 16.3 et 16.7 (4 C H 3 ); 22.7 et 22.9 (2 C H 2 ); 27.4 et 28.2 (( C H 3 ) 3 C et 2 C H 2 ); 30.8 (2 C H 2 ); 38.7 et 39.0 (2 C H 2 N); 48.1 (O C H 3 ); 48.8, 50.0, 50.1, 51.4, 53.7 et 55.7 (4 C H Ala et 2N C H Lys); 68.2 et 68.5 (2C 6 ); 70.2 et 70.7 (C 5 ); 72.4 (2O C H 2 Bn); 72.6 (C 4 );73.0 (2O C H 2 Bn); 74.4 (2O C H 2 Bn); 74.9 (C 2 ); 75.0 (2O C H 2 Bn); 79.7 ((CH 3 ) 3 C ); 80.3 (C 3 ); 96.2 (t, 27 Hz, C 1 );127.3-128.1 ( C ar.); 138.0-138.9 ( C ar. quat.); 157.0 ( C O(Boc));160.2 (t, 28 Hz, CF 2 C ONH); 172.5, 173.1, 173.2, 174.1 et 174.5 ( C ONH et C O 2 Me).
Mass (MALDI+): 1929 (M+Na); 1945 (M+K)
E) Deprotection of the N- Then O-Terminal Functions of the Dimer 27 Obtained ( FIGS. 18 and 19 ):
In a flask under an inert atmosphere containing starting product 27 (107 mg; 0.6 mmol; 1 eq.) in dichloromethane (2 mL) the addition is made of trifluoroacetic acid TFA (89 μL; 1.2 mmol; 20 eq.). The mixture is left to react for 12 hours then the reaction medium is concentrated. Four to five co-evaporations with toluene are performed to obtain product 28 in the form of colourless oil with quantitative yield.
Characterization of Product 28:
C 99 H 117 F 7 N 8 O 23 M=1920.02 g.mol −1
19 F NMR (CD 3 OD, 282.5 MHz)
−77.4; −120.2.
1 H NMR (CD 3 OD, 300 MHz)
1.3 (m, 12H, 4C H 3 ); 1.3-1.7 (m, 12H, 6C H 2 ); 3.0 (m, 4H, 2NHC H 2 ); 3.5 (m, 4H, H 6 ); 3.5 (s, 3H, OC H 3 ); 3.7 (m, 1H, C H NH (Lys)); 3.8 (m, 4H, H 3 ; H 4 ); 4.0 (m, 2H, H 5 ); 4.2-4.8 (m, 23H, 8OC H 2 Bn, 4C H (Ala), C H NH (Lys), 2H 2 ); 7.2 (m, 40H, H ar.).
In a flask containing starting product 28 (115 mg; 0.06 mmol; 1 eq.) in THF (2 mL), the addition is made of lithine LiOH (6 mg; 0.24 mmol; 4 eq.) in solution in minimum of water. The mixture is left to react 12 hours then collected in dichloromethane. A 1N solution of hydrochloric acid HCl (4 mL) is added and the aqueous phase is extracted three times with dichloromethane. The organic phases are collected, washed in water (4 mL) then concentrated.
Four to five co-evaporations with toluene are conducted to remove water traces and obtain product 29 in the form of a white solid with a yield of 89%.
Characterization of Product 29:
C 96 H 115 ClF 4 N 8 O 21 M=1828.43 g.mol −1
19 F NMR (CD 3 OD, 282.5 MHz)
120
1 H NMR (CD 3 OD, 300 MHz)
1.3 (m, 12H, 4C H 3 ); 1.3-1.7 (m, 12H, 6C H 2 ); 3.0 (m, 4H, 2NHC H 2 ); 3.5 (m, 4H, H 6 ); 3.7 (m, 1H, C H NH (Lys)); 3.9 (m, 4H, H 3 ; H 4 ); 4.1 (m, 2H, H 5 ); 4.2-4.8 (m, 23H, 8OC H 2 Bn, 4C H (Ala), C H NH (Lys), 2H 2 ); 7.2 (m, 40H, H ar.).
F) Debenzylation of the Galactoside Units ( FIG. 20 ):
A flask containing starting product 29 (90 mg; 0.05 mmol) in a mixture of acetic acid CH 3 CO 2 H (2.5 mL), tetrahydrofurane THF (0.8 mL) and water (0.8 mL) in the presence of a spatula tip of palladium on charcoal Pd/C is placed under a hydrogen atmosphere. The mixture is left under stirring overnight then filtered on a Millipore® filter. The mixture is concentrated to obtain product 30 in the form of a white solid with quantitative yield.
Characterization of Product 30:
C 40 H 67 ClF 4 N 8 O 21 M=1107.45 g.mol −1
1 H NMR (D 2 O, 300 MHz)
1.5 (m, 12H, 4C H 3 ); 1.7-2.0 (m, 12H, 6C H 2 ); 3.4 (m, 4H, 2NHC H 2 ); 3.7-4.5 (m, 18H, 2H 6 , C H NH (Lys), 2H 3 ;2H 4 , 2H 5 , 4C H (Ala), C H NH (Lys), 2H 2 ); 7.2 (m, 40H, H ar.).
13 C NMR (D 2 O, 75.5 MHz)
16.9 et 17.0 (4 C H 3 ); 21.7 et 22.6 (2 C H 2 ); 27.9 et 30.8 (4 C H 2 ); 39.3 et 39.6 (2 C H 2 N); 49.6, 49.8 et 50.0 (4 C H Ala); 53.2 et 53.8 (2N C H Lys); 61.1 et 62.6 (2C 6 ); 67.1, 68.9, 70.6, 70.9, 72.4, 73.9, 75.5 80.2 (2C 5 , 2C 4 , 2C 2 , 2C 3 ); 173.9, 174.5 et 175.1 ( C ONH et C O 2 Me).
Masse (ESI+): 1071 (MH+); 1093 (M+Na); 1109 (M+K)
The invention is not restricted to the previously described examples.
The synthesis of a compound belonging to the general formula I, bearing a diaminoacid unit AA 1 -AA 2 in R 4 , will be easily obtained via two different processes using very classical chemical reactions already described in this text:
starting from the glycopeptide 12 or 22, after deprotection of the NBoc moiety, the coupling reaction with the carboxylic function of the AA 1 -AA 2 will lead to the desired compound after the usual N,O deprotection and debenzylation of the sugar unit. the introduction of the diaminoacid AA 1 -AA 2 can also be done on a previous step and especially on the peptide 21 or 25 after deprotection of the Nboc via usual coupling reaction.
Then the deprotection of the side chain of the Lysine, and the coupling reaction with the carbohydrate derivatives 16 will give the glycopeptides after the usual deprotection steps.
Preliminary Preservation Tests of Biological Materials
Preliminary biological tests were conducted on the glycoproteins and notably the synthesized products. They enabled us to determine the effect of these compounds on different cell cultures at different temperatures and for varying periods of time. The purpose being to observe whether these compounds have a protective effect on cells.
The compounds 15 and 30 may be named in the following part AAGP or AFGP.
A) Effects of Product 15 on the Preservation of HEK 293 Kidney Cells
HEK 293 cells were cultured to 100% viability in a 75 cm 2 culture dish. The cells were then diluted to 75,000 cells/mL. Subsequently they were distributed over 6 plates with six 3 mL-wells per plate. This concentration is a good compromise between a concentration sufficiently low to prevent cell death by autocytotoxicity and sufficiently high to permit cell sampling and counting without any pre-concentration likely to reduce their survival. Each plate had two control wells not containing product 15, two wells with concentrations of product 15 adjusted to 0.01 mg/mL, and two others with 0.1 mg/mL. Each plate was then incubated at the following temperatures: 4° C., 2° C., 0° C., −2° C., −4° C., and −20° C. Each well was subsequently sampled at the following incubation times: 2, 8, and 22 hours.
Materials
HEK 293 cells (Graham et al.) DMEM cat # D5671, Sigma Trypsin, Cat# 25-052-CI, MultiCell PBS, Cat#SH30028.02, HyClone Trypan Blue Cat# 72-57-1
Consumables
Micropipette tips, 200 μL, Axygen 6 well plates for cell culture, cat#353046, Falcon T-Flask for cell culture75 cm2, cat #430725, Corning Pipettes, 2 mL, 5 mL, 10 mL and 25 mL, Falcon
Equipment
Refrigerator, Danby Freezer, Frigidaire Incubator, Sanyo Microscope, Zeiss Inverted microscope, Olympus Bench-top centrifuger, IEC Hemocytometer, Rechter Traceable digital thermometer, Fisher Scientific Thermometers, VWR Cell Counter, No. 8-004, HOPE
Results
Cell counts showed that duplicated experiments are coherent with each other, since the differences do not exceed 10% with a sole exception showing a variation of 13%.
The cell cultures used to start the experiment were 100% and their morphological characteristics under the microscope showed good condition.
At five of the six tested temperatures ( FIGS. 21-26 ), the presence of product 15 at 0.10 mg/mL (the highest concentration used for this experiment) led to the best cell survival rates even if the improvement remained low. The concentration of 0.01 mg/mL of product 15 does not appear to improve cell survival in comparison with the negative control.
At −20° C., after two hours, all the wells were frozen and the media had a gelatinous appearance. After thawing, microscopic observation showed that the control cells have a phantom appearance and immediately absorb Trypan blue, whilst the cells with compound 15 maintained the appearance of spherical retractile cells and did not absorb Trypan blue similar to living cells. Therefore, cell structure and morphology and some permeability functions were maintained in the presence of product 15 which was not the case with the control.
After this thawing, the plates were re-incubated at −20° C., but similar procedure after eight hours' incubation led to complete disappearance of all cells for both concentrations of product 15.
B) Effects of Product 15 on the Preservation of Erythrocytes.
The death of erythrocytes can be ascertained by rupture of the plasma membrane. This phenomenon is called haemolysis. Detection of haemolysis is the chief tool used in this experiment to determine the effect of product 15 at different temperatures on the preservation of erythrocytes.
Plan of Experiment
Blood sampling→Aliquots→Addition of AAGP (compound 15)→Various temperatures→Observation of haemolysis
Product 15 was tested at concentrations of 0 mg/mL, 0.1 mg/mL, 1.0 mg/mL at temperatures of 3, 0, −3, −5, −10, −15, −23, −78° C.
From a sample of human blood in a borosilicate heparinized tube, microtubes of 275 μL were filled to full capacity. One third of the microtubes were completed with 2.75 μL of product 15 (10 mg/mL in H 2 O), and one third of the microtubes were completed with 27.5 μL of product 15 (10 mg/mL in H 2 O). The blood was divided among the tubes to full capacity to prevent air contact as much as possible.
The microtubes were incubated at different temperatures for different periods ranging from 2 to 9 hours. The microtubes were frozen on a microtube support and the experiment was conducted using a slow-freeze apparatus at −78° C., whilst thawing was always conducted at room temperature on the microtube rack. After thawing, the microtubes were delicately homogenized by inverting a few times and a sample of erythrocytes was taken. The erythrocytes (Ery) were diluted in PBS 500× and 2× in Trypan Blue before observation and before obtaining the haemolysis percentage such as defined in this equation:
% Haemolysis=[1−( Co−C exp)]*100
in which: Co is the initial Ery count
Cexp is the experimental Ery count
Materials
15 mL human blood sample in borosilicate heparinized tube PBS, Cat#SH30028.02, HyClone Trypan Blue, Cat# 72-57-1
Consumables:
Micropipette tips, 200 μL, Axygen 200 μL PCR microtubes 2 sterile heparinized tubes, Cat# 366480, Becton-Dickinson
Equipment:
Fisher Isotemp low temperature Incubator, Fisher Scientific
Refrigerator, Danby
Freezer, Frigidaire
Ultra-Low temperature Freezer
Slow-rate freezing device, Nalgene
Microscope, Zeiss
Digital camera, Olympus
Hemocytometer, Rechter
Traceable digital thermometer,
Fisher Scientific
Thermometers, VWR
Cell Counter, No. 8-004, HOPE
In table 1, it can be seen that there is no haemolysis in the temperature range of 2 to −10° C. The erythrocytes appear to remain intact from 0 to 24 hours after incubation at these temperatures whether with or without product 15.
TABLE 1
% Haemolysis vs. Incubation Time at Different Concentrations
of product 15 and at 3, 0, −3, −5 and −10° C.
Conc. Product
Incubation
15 (mg/mL)
Time (h)
% Haemolysis
% Ery
0.0
0
0
100
0.0
2
0
100
0.1
0
100
1.0
0
100
0.0
4
0
100
0.1
0
100
1.0
0
100
0.0
9
0
100
0.1
0
100
1.0
0
100
0.0
24
0
100
0.1
0
100
1.0
0
100
The blood samples were placed at −15° C. for the same times. In table 2, after two hours, it can be seen that product 15 partly protects the erythrocytes at a concentration of 0.1 mg/mL and completely at 1.0 mg/mL. At 4 and 9 hours, complete protection is only obtained with a concentration of 1.0 mg/mL.
TABLE 2
% Haemolysis vs. Incubation Time at Different
Concentrations of product 15 at −15° C.
Conc. Product
Incubation
Number of
15 (mg/mL)
time (h)
erythrocytes
% Haemolysis
% Ery
0.0
0
123
0
100
0.0
2
0
100
0
0.1
90
27
73
1.0
120
2
98
0.0
4
0
100
0
0.1
0
100
0
1.0
133
0
100
0.0
9
0
100
0
0.1
0
100
0
1.0
121
2
98
More extreme conditions were also tested. At −23° C. and −78° C., the erythrocytes ruptured if these temperatures are reached rapidly.
Therefore, a test was conducted using slow cooling to reach −78° C. A blood sample without product 15 was incubated for different times to determine the freezing point. As can be seen in table 3, the freezing point is reached after 40 minutes. At this instant a direct correlation is observed between % haemolysis and concentrations of product 15.
TABLE 3
% Haemolysis vs. Different Concentrations of product
15 at −78° C. with slow cooling
Conc. Produit
%
%
15 (mg/mL)
Time (min)
Haemolysis
erythrocytes
0.0
0
0
100
0.0
15
0
100
0.0
35
0
100
0.0
40
0
100
0.1
36
64
1.0
97
3
0.0
50
100
0
In most cases, except after 2-hours incubation at −15° C., either complete or no haemolysis at all is observed. It is evident that the haemolysis process is very rapid and occurs on freezing. The fact that at a temperature below −15° C., no protection is observed by product 15 at 1.0 mg/mL, may mean that this compound protects the erythrocytes by reducing the freezing process rather than by stopping it, at least with concentrations of 1.0 mg/mL. The phenomenon of crystallization leads to rupture of the erythrocyte membranes. However, by decreasing the time (less than two hours) it could be gained more details on the dynamics of haemolysis in the vicinity of the freezing point. It is observed however that product 15 really protects the erythrocytes at −15° C.
C) Effects of Product 15 on the Preservation of Blood Platelets.
The purpose is to test product 15 on the preservation of blood platelets to improve current protocols which only allow their preservation for 5 days. The test was conducted at four different temperatures 22° C., 15° C., 4° C. and finally 0° C. Platelet follow-up lasted 21 days to examine platelet clustering. Clustering is one of the first and most definitive indicators of platelet degradation. During their degradation, the platelets become active, lose their morphology, become fibrous, form clusters and finally degenerate. A platelet count is made but the result is rather more based on the extent of clustering.
FIGS. 27 and 29 show a positive effect on platelet clustering due to the presence of product 15. In FIG. 27 , at 22° C., the results (negative control, 1 mg/mL and 4 mg/mL of product 15) are compared. It is observed that almost immediately (after two days), clustering starts to occur in the control and continues to increase, whereas the samples with glycoprotein 15 do not show any clusters before up to 7 days. In the course of time at 13, 17 and 21 days a much more marked difference is seen and hence a true inhibition of platelet clustering by product 15. It is the most concentrated samples (4 mg/mL) which show the least clustering.
FIG. 28 at 15° C. shows the same type of results as previously. Clustering at this temperature starts becoming notably apparent after 4 days. Over time, a greater increase in clustering is observed in the control than in the samples containing the compound. However there are fewer clusters at this temperature than at 22° C.
At 4° C. ( FIG. 29 ), almost no clustering is observed with product 15 irrespective of concentrations. In the control, the number of clusters is also markedly lower than at the other temperatures.
At 0° C. no clustering is seen, whether with or without glycoprotein 15.
D) Effects of Products 15 and 30 on the Preservation of Heart Myoblasts.
The purpose of this experiment was to examine the effect of gem-difluoro glycoproteins on the cells of heart tissue, and also to make a comparison between the monomer (product 15) and dimer (product 30) of synthesized compounds.
The test was conducted on rat heart myoblasts to consider application of these compounds for the preservation of organs such as the heart for subsequent transplant.
Preliminary Experiment
1) The cells are thawed and cultured until doubling is stable in DMEM medium, at 5% CO 2 and 37° C.
2) The cells are amplified in a flask.
3) 300 μL with 100 000 cells are divided among the microtubes
4) 3 μL PBS is added to a negative control tube
5) In three microtubes 0.3, 1.5 and 3 μL of 100 mg/mL of product 15 are respectively added to obtain a concentration of 0.1, 0.5 and 1 mg/mL,
6) In three microtubes 0.3, 1.5 and 3 μL of 100 mg/mL of product 30 are respectively added to obtain a concentration of 0.1, 0.5 and 1 mg/mL.
6) The cells are incubated at −2° C.
7) The cells are sampled at 0, 2, 7, 20 and 43 hours after incubation.
Main Experiment
1) The cells are amplified in a flask
2) 300 μL with 100 000 cells are divided among the microtubes
3) 3 μL PBS are added to four negative control tubes
4) In four tubes 3 μL of product 15 are added to obtain 1 mg/mL
5) In four tubes 3 μL of product 30 are added to obtain 1 mg/mL
6) A set of tubes (Control-Monomer-Dimer) is incubated at room temperature (22° C.)
7) A set of tubes (Control-Monomer 15-Dimer 30) is incubated at 4° C.
8) A set of tubes (Control-Monomer 15-Dimer 30) is incubated at −3° C.
9) A set of tubes (Control-Monomer 15-Dimer 30) is incubated at −10° C.
10) Each tube is sampled to count living and dead cells at 0, 8, 16 and 22 hours after incubation
11) Only the tube of monomer 15 at −3° C. is sampled at 0, 8, 12, 16, 20 and 22 hours for the count of living and dead cells.
Materials
H9c2(2-1) cells, ATCC Number CRL-1446, adherent cell line derived from rat myocardial tissue (1, 2, 3) DMEM 4 mM L-Glutamine Incubators, 37, 22, 4, −3, −2 and −10° C. Pipetters Micropipette tips Hemacytometer Trypan Blue Microscope Cell counter Microtubes Microtubes rack
For the Preliminary Experiment:
For monomer 15 at 2° C. ( FIG. 30 ), the survival percentage is very close to 100% with all concentrations at 0, 2 and 7 hours. At 20 hours, this percentage decreases to 44% for 1 mg/mL, to 28% for 0.5 mg/mL while 0.1 mg/mL is identical to the control. This leads to supposing a protective effect dependent upon the concentration of glycoproteins.
For dimer 30 ( FIG. 31 ) using the same procedure, identical results are observed. After 20 hours, the cell survival percentage is 25% at 1 mg/mL, 11% at 0.5 mg/mL and 6% at 0.1 mg/mL.
When the two glycoproteins are compared in parallel ( FIG. 32 ), the most significant result is with 1 mg/mL for which a protective effect of the two compounds 15 and 30 is observed on the cells after 20 hours with 44% survival for monomer 15 and 25% for dimer 30, compared with only 8% for the control.
For the Main Experiment:
This is performed with 1 mg/mL concentrations of monomer 15 or dimer 30 at 4 different temperatures: 22, 4, −3 and −10° C. There is no significant difference for up to 8 hours at all temperatures ( FIG. 33 ). After 16 hours ( FIG. 34 ), a strong correlation is observed between the presence of glycoprotein and cell survival percentage compared with the negative control at temperatures of 4 and −3° C. Unfortunately these results do hot make it possible for a conclusion to be drawn as to which of the two forms has the best protective effect; at 4° C. it is monomer 15 which gives the best results, while at −3° C. it is the dimer 30. After 22 hours ( FIG. 35 ), there is a major fall in the number of living cells. However, at −3° C., the dimer form is noted to have an effect with a survival percentage of 17%.
At 22° C. ( FIG. 36 ), after 45 hours, a 51% survival is observed in the control while the monomer 15 and dimer 30 only fall to 65 and 80% respectively.
The same type of curve is obtained at 4° C. ( FIG. 37 ), with a final result that is less convincing at 45 hours, but showing a better survival percentage over the entire duration of the experiment for the monomer. At −3° C. ( FIG. 38 ), the result is similar with the dimer, especially in the range of 8-22 hours.
At −10° C. ( FIG. 39 ), similar results are observed for the dimer and the control, and a slight improvement for the monomer.
FIG. 40 , at −3° C., shows the slow decrease over incubation time in the number of living cells with the presence of the monomer.
During these experiments on myoblasts, it was found that the monomer and dimer compounds have a protective effect on these cells. It appears that:
There exists a correlation between the increase in concentration of glycoproteins 15 and 30 and cell survival rate, monomer 15 and dimer 30 giving better results at 1 mg/mL than at 0.1 and 0.5 mg/mL. The effect is only seen to be marked after 8 hours. All the experiments show results of interest essentially between 8 and 20 hours. The protective effect of most interest is apparent at 4° C. and −3° C. It is impossible to confirm whether it is the monomer or dimer which is the most active.
Another test was conducted on myoblasts at temperatures of 3° C. and −3° C. The purpose of the experiment this time was to increase the concentrations of glycoproteins 15 and 30 equimolar fashion (the molecular weight of the dimer being 2× greater than that of the monomer). The increase in concentration was 2.5 mg/mL for monomer 15 and 5 mg/mL for dimer 30. The temperatures were chosen over a range frequently used for the preservation of cells and tissues. The idea being subsequently to continue this experiment directly on tissues.
Method
1) The cells are expanded in a flask.
2) Three tubes with 1.0 mL cells are prepared with 0.2×106 cells/mL
3) To one tube, 25 μL of monomer 15 at 100 mg/mL are added to obtain 2.5 mg/mL (4.3 mM)
4) To another tube, 50 μL of dimer 30 at 100 mg/mL are added to obtain 5.0 mg/mL (4.5 mM)
5) The tubes are sampled in plates of 2×96 wells with 100 μL per well
6) One plate is incubated at 3° C. and the other at −3° C.
7) The count of living and dead cells is made at 0, 8, 12, 16, 20 and 24 hours.
FIGS. 41 and 42 give the cell survival rate in the negative control, in the presence of monomer and dimer at 3° C. and −3° C. after 8, 12, 16, 20 and 24 hours.
According to FIGS. 41 and 42 the heart cells survive longer at −3° C. than at 3° C. After 24 hours, there is no survival at 3° C. whereas at −3° C. with the dimer a survival rate of 70% is observed.
In most cases, the monomer gives the same results as the dimer. FIG. 42 shows that at 3° C. the control falls to a survival rate of 19% after 8 hours, whereas it remains more than twice as high with the monomer and four times more with the dimer. AAGP therefore extends the survival of heart cells especially between 8 and 12 hours, but also up to 24 hours.
In FIG. 43 , the data from the preceding experiment at 1 mg/mL have been combined with the largest concentrations used for this experiment. These compounds 15 and 30 have greater efficacy at higher concentrations.
These results highlight the protective role of products 15 and 30 on cell survival in relation to concentration. The results of most interest appear in FIGS. 41 and 42 . After 24 hours, approximately 75% of the myoblasts are still living with the dimer and 65% with the monomer, whereas only 30% remain in the control. Even after 16 hours, the monomer and dimer preserve approximately 90% of the cells.
In addition when the concentration of glycoproteins increases, cell survival is the same whether for the monomer or the dimer ( FIG. 43 ).
The results therefore show that the cells derived from myoblasts are viable when preserved at low temperature in the presence of products 15 and 30.
E) Effect of Product 15 on the Preservation of Skin Fibroblasts
The purpose is to test product 15 on skin fibroblasts at different temperatures.
1) The cells are thawed and cultured until doubling is stable in DMEM medium with 5% CO 2 at 37° C. 2) The cells are amplified in a Petri dish 3) Cell concentration is brought to 0.27×10 6 cells/mL 4) 1.8 mL of cell suspension are completed with 90 μL AFGP mother solution at 100 mg/mL and evenly distributed in four cell culture plates, 100 μL per well. 5) 1.8 mL of cell suspension are completed with 90 μL of PBS solution and uniformly distributed over 4 cell culture plates, 100 μL per well. 6) One plate is incubated at 22° C., another at 3° C., another at −3° C., and the final plate at −20° C. 7) The cells are sampled at 8, 12, 20 and 30 hours to follow up cell viability using the Trypan Blue exclusion technique.
Materials
Cells CCD-27Sk, ATCC Number CRL-1475, Adherent normal fetal
fibroblast skin cells from human (1)
DMEM 4 mM L-Glutamine
Incubators, 22, 3 and −3° C.
Pipetters
Micropipette tips
Hemacytometer
Trypan Blue
Microscope
Cell counter
Microtubes
Microtubes rack
Cell culture plate, Costar 96-wells, flat bottom, non-treated for cell
culture.
In FIG. 44 , no difference is found between the cells preserved with or without product 15 over the entire temperature range. However, at −20° C. the samples freeze leading to death of the cells after thawing.
After 12 hours, still no major difference is seen over the range 22° C., 3° C. and −3° C., on the other hand better preservation is seen to occur with compound 15 at 22° C. and −3° C.,
In FIG. 46 , results show a better cell survival rate with monomer 15 than with the control. Nonetheless, at −3° C., the survival rate decreases to 50% even in the presence of the monomer. After 30 hours ( FIG. 47 ), the cells protected by product 15 show a distinct improvement especially at 3° C. At −3° C., even if the presence of the compound improves survival, it is reduced to 70%.
If the trend over time is followed at the same temperature ( FIGS. 48 to 50 ), it is noted that the control shows a rapid decrease in survival at −3° C., a decrease at 3° C. and a slow decrease at 22° C. The same type of pattern is found in the presence of product 15 but, by comparison, with much better survival rates.
The use of 5 mg/mL monomer 15 corresponds to 8.6 mM. This is the first experiment we have conducted at said concentration and results are extremely positive in that the skin fibroblasts show better preservation in the presence of product 15 at all temperatures except at −20° C. when the cells freeze and die whether or not the monomer is present. The best improvements are found at 3° C.
It was therefore decided to work at 3 and −3° C. but with higher concentrations of compound 15 of up to 15 mg/mL.
FIGS. 51 and 52 clearly indicate that the increase in concentration of product 15 improves cell survival rate at 3 and −3° C. These results show that compound 15 has a strong protective effect on cells that is close to 100% even after 34 hours.
The potential of these compounds (10 mg/mL) was also assessed on fibroblasts at 37° C. and 15° C., which could be of interest for the application of these compounds in cosmetology.
In this experiment, the aim was to study the efficacy of gem-difluoro glycoproteins under physiological conditions:
Compound 15 preserves approximately 100% of cells at 37° C. even after four days, whereas in the control the survival rate is 20%. This show a strong protective effect under physiological conditions ( FIG. 53 ).
The monomer 15 also preserves cells (46% survival) at 15° C., whereas only 11% are found in the control after four days ( FIG. 54 ).
The cells incubated with this compound preserve a spherical shape and maintain their integrity, whereas in the negative control the cells lose their structural morphology and become adherent ( FIG. 55 ).
Preliminary Results on the Protection of Adult Primary Skin Fibroblasts By Compound 15
The preceding results have shown that the monomer 15 has a strong protective effect on embryonic skin fibroblasts over a varied temperature range. This test was extended to adult primary fibroblasts. In the following study, experiments were conducted at 15° C., 3° C., on adult fibroblasts, but also at 37° C. under H 2 O 2 on embryonic fibroblasts.
Experimental Protocol
Culture Conditions:
For adult fibroblasts, a culture medium (rich in factors) is used,
For embryonic fibroblasts, a serum-free medium with 0.5 mM EDTA is used to prevent clustering. The cells are treated with 1 mM H 2 O 2 to induce oxidizing stress. Samples are examined at 0, 1, 2, 3, 4 and 6 days for the experiments on adult fibroblasts, and at 2 and 10 hours on embryonic fibroblasts. The concentration of product 15 is 15 mg/mL.
On the Adult Primary Fibroblasts:
At 15° C. ( FIG. 56 ), compound 15 protects 100% of cells even after six days, whereas almost all the control cells are dead. At 3° C. ( FIG. 57 ), 100% survival is also observed, and only 9% after six days in the control.
On the Embryonic Fibroblasts:
The monomer 15 protects the cells with approximately 80% survival, compared with the control in which the cells are all dead after 10 hours ( FIGS. 58 and 59 ). The difference is clearly seen between the cells treated with AAGP and the control (living cells shown in green, dead cells in red). Product 15 can therefore act as protective agent against oxidizing stress, a major problem in skin ageing and skin diseases.
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The invention concerns a gem-difluorinated C-glycopeptide compound of formula (I)
in which N is an integer between 1 and 5, R 4 =H, AA 1 , AA 1 -AA 2 and R 5 =OH, AA 1 , AA 1 , AA 2 , with AA 1 , and AA 2 are independents groups and represent amino acids with a non-functionalized side chain and R 1 , R 2 , R 3 are independent groups and one of them is equal to formula (II), in which n is an integer between 3 and 4, Y, Y′ are independent groups in which Y, Y′=H, OR, N 3 , NR′R″, SR″′, where R=H, benzyl, trimethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, acetate group, R′, R″′═H, alkyl, allyl, benzyl, tosylate group, C(═O)-alkyl, C(═O)−Bn, R″′=H, alkyl, acetate group, R 6 is notably a group H, CH 3 , CH 2 OH, CH 2 -Glycoside group, CH 2 -OGP in which GP is a protector group such as an alkyl, benzyl, trimethylsilyl, tert-butyldimethylsilyl, tertbutyldiphenylsilyl, acetate group,; and R 7 =OH, OGP′, NH 2 , N 3 , NHGP′, NGP′GP″ in which GP′ and GP″ is or not a protector group such as an alkyl, benzyl, trimethylsilyl, tertbutyldimethylsilyl, tert-butyldiphenylsilyl, acetate group, and R B is a hydrogen atom H or a free or protected alcohol function. It applies notably to preservation of biological materials and to cryosurgery.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related to co-filed applications, "Ferrule Buckle with Sliding Release Button", Robert L. Stephenson, and "Improved Ferrule Buckle", Per Olaf Weman,
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a buckle and tongue combination of the type used in automobiles, airplanes and other vehicles, for retaining an occupant in a seated position within the vehicle at a moment of rapid deceleration. With many of these the buckle is attached to the frame or body of the vehicle by a relatively short rigid or semi-rigid connector, and the cooperating tongue is attached to one or two flexible passenger restraints disposed over the lap, or the lap and chest of the user. In other passenger restraint systems, both tongue and buckle are attached to flexible restraints. Generally the tongue is inserted into the buckle and latched, thereby securing the restraining system about the passenger. Various means have been devised to release the latched tongue. Release of the tongue is effected by lifting the cover of the buckle or depressing a button on its upper surface. This action forces the latching member out of engagement with the tongue, permitting the tongue to be removed from the buckle.
2. Description of the Prior Art
A large number of such buckle and tongue combinations are found in the prior art, practically all of which incorporate a buckle having some type of latching means co-acting with the tongue. Many of these have an independent latching member within a cast metal or predominantly plastic housing, and frequently the connection between the release button or lever, and the latching member, is indirect.
It is an object of the present invention to provide a rugged and functional safety buckle and tongue combination which cannot be unlatched by the application of stress, yet a buckle wherein the tongue can be released by the application of a minimal effort by the user, even when the buckle is under stress.
It is a further object of this invention to provide a buckle wherein the strength of the connection between the tongue at one end and the attached passenger restraint at the other, is independent of the housing or the secondary components. In the buckle of this invention the tongue is not only latched, but locked to the ferrule, and the ferrule is fixedly attached to a passenger restraint such as a steel cable. The connection is both simple and reliable.
SUMMARY OF THE INVENTION
The present invention is directed to a positive-acting buckle and tongue combination. The basic structure is an elongated ferrule. By the term "ferrule" we mean an elongated metal member which constitutes the connecting link between the tongue at one end and the passenger restraint at the other.
The shape of the ferrule is not critical, but preferably the ferrule is cylindrical.
In the buckle of the present invention the tongue latches to the ferrule so that a direct connection is had between the tongue and the restraint attached to the ferrule. Preferably the components making up this direct connection, namely the tongue, the latch pin and the tongue release lever are fabricated of metal. The remaining components which include the housing, the sheath for the ferrule when this component is used, and the tongue ejector, may also be metal, but preferably they are fabricated of a polymeric material. The use of such materials for these components reduces the weight of the buckle without loss of strength for they are under substantially no strain or tension. They also contribute to the smooth action of the moving parts.
Briefly, the buckle and tongue in combination comprises, first, the ferrule having a passenger restraint fixed at one end, and a through slot at the other for engaging the tongue. An opening extends at least into the slot from the surface of the ferrule, said opening being perpendicular to the plane of the slot. Preferably this opening continues through the first, and well into the second arm of the ferrule. It may continue entirely through the two arms on each side of the slot, being an opening, preferably cylindrical, passing through the slotted portion of the ferrule and perpendicular to the slot.
A pin is slideably positioned in the opening, piston-like, and biased downwardly for engaging an opening in the tongue situated to accept the pin when said tongue is inserted into the slot. The means employed can be a first order lever, one leg comprising a push button, accessible through an opening in the housing; the other leg extending beyond the fulcrum, engaging the upper portion of the pin. With this arrangement, downward pressure on the push button end of the lever produces an upward movement of the engaged pin against its bias. When the fulcrum is closer to the point of engagement with the pin than with the push button, a mechanical advantage is obtained for raising or extracting the pin from the opening in the tongue.
There are several ways in which the lever may engage the pin. The end of the lever can be a bifurcation to lift the pin by acting beneath a head on the pin. A reduction in the circumference of the pin near the top can similarly provide a purchase for such a bifurcation. Alternately, the pin may be raised by the sloping surface of an inclined plane, hereafter referred to as a wedge. The pin can have at its upper end, projections on opposite sides extending toward the sides of the buckle. These projections contact the sloping surfaces of two wedges, one on each side of the pin, whereby pressure on a outwardly biased sliding push button to which the wedges are attached, raises the pin out of the slot in opposition to its bias. The projections referred to can be the ends of biasing springs inserted into the corresponding openings in the upper part of the pin to provide the downward bias. Decreasing the slope of the wedges increases the degree of mechanical advantage they provide for raising the pin.
A tongue ejection member is provided, having a flat portion for sliding reciprocating action within the slot of the ferrule, and biased outwardly to a stopping point directly below the pin.
In operation, when the tongue is inserted, it contacts the tongue ejector to force it back in opposition to its bias, freeing the pin to drop, in response to its bias, into the opening of the tongue, thereby securely latching it to the ferrule. When the pin is raised, the tongue ejection member slides forward in the slot in response to its bias, forcibly ejecting the tongue, and stopping directly beneath the raised pin, retaining it above the slot until the tongue is reinserted.
In one embodiment of our invention, the ferrule is enclosed in a cylindrical sheath which can be integrated with the front face of the buckle housing. Slotted openings correspond with the sides of the slot of the ferrule, allowing freedom of motion to the tongue ejector. An opening also coincides with that in the top of the ferrule for the pin. A fulcrum can either be provided on the top of the sheath, or outward extensions on the side, or openings for a shaft extending through the ferrule, can provide journals for legs extending from the lever, to thus provide the fulcrum.
A better understanding of the operation of the buckle and tongue in combination of the present invention may be had by reference to the accompanying drawings wherein like reference characters refer to like parts throughout the several views.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded view of one embodiment of the seat buckle and tongue combination of the present invention.
FIG. 2 is an enlarged cross section in elevation of the assembled buckle of FIG. 1 with tongue inserted and securely latched into position by a pin.
FIG. 3 is an enlarged cross section similar to that of FIG. 2 except that the push button has been depressed, ejecting the tongue. The ejector now supports the biased pin above the slot permitting the tongue to be reinserted.
FIG. 4 is an enlarged perspective view of the biased push button, the pin and the sheath for enclosing the ferrule, of an embodiment differing slightly from that of FIG. 1. Here the push button pivots on projections at the side of the sheath rather than at a fulcrum on its top surface. These projections can be the ends of shafts extending part way, or all the way through the ferrule within.
A single trifurcated flat metal spring attached to the frame of the push button has been substituted for the two flat springs of FIG. 1.
FIG. 5 is an enlarged perspective break-away view of a slide push button, a biased latching pin, a ferrule, a tongue ejector and a tongue ejector spring of still another embodiment of the seat buckle and tongue combination of the present invention. This embodiment differs only slightly from the buckle of FIG. 1. The pin, as before, is biased downwardly, but here the pin is lifted out of engagement with the tongue by two wedges with can be pressed under the upper part of the springs that bias the pin downwardly. A single coiled ejector spring which operates in a cylindrical longitudinal chamber, concentrically positioned within the ferrule, replaces the two external ejection springs used in the embodiments of FIGS. 1 and 4.
FIG. 6 is an enlarged cross-section in elevation of the assembled buckle of FIG. 5 within a housing. The tongue has been inserted and securely latched by the pin. All three embodiments are similar in that they have a ferrule with a through slot and a pin operating within a cylindrical opening perpendicular to the slot for engaging a corresponding opening in an inserted tongue. Also, in each case the pin is lifted by pressing a button, and the pin is retained in its unlatched position by the tongue ejector, after the tongue is ejected. In each embodiment the tongue ejector is slideably positioned in the slot, is biased outwardly, and is stressed for ejecting the tongue by the very act of inserting the tongue.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference to the six figures, our invention is directed to a safety seat buckle and tongue in combination comprising a ferrule 1 provided with means at its front end for engaging or disengaging a tongue 2, and at the other end, means for the fixed attachment of a seat belt or other restraint.
By the term "ferrule" we mean in this instance, a connecting member which forms the link between the tongue when engaged therein, and a cable, belt or other restraint which may be flexible, semi-rigid or rigid.
In the embodiments of the drawings, the ferrule 1, preferably fabricated of metal, receives tongue 2 at its front end, and is attached to a restraining cable or shaft, the receptacle for which is shown as 3.
In the front of the ferrule there is in the case of each of the three embodiments shown, a parallel sided through slot 4 which may be centered as in FIG. 1 or placed off-center as in FIGS. 5 and 6. The slot is sized to accept the forepart of tongue 2. A short distance from the front end of the ferrule there is a cylindrical opening 5 extending from either the upper or lower surface of the ferrule, substantially perpendicular to the surfaces of the slot and of the tongue when inserted. This cylindrical opening extends at least to the slot, and preferably extends beyond the slot into the substance of the ferrule. If desired, the opening may extend entirely through the ferrule.
Tongue 2 also has an opening 6 in its forward section, so positioned, that when the tongue is inserted into the slot, the opening in the tongue substantially coincides with the cylindrical opening 5 and therefore constitutes a port or continuation of that opening.
A cylindrical pin 7 is provided with sufficient clearance to easily move piston-like slideably through the cylindrical opening 7. The diameter of the upper portion of this pin may be reduced, leaving a head 8 as in FIGS. 1, 2 and 3. It may be uniformly cylindrical but having a head as in FIG. 4, or it may be uniformly cylindrical with openings near the top as in FIGS. 5 and 6. There are of course many other variations in the form of pin 7 which would equally as well provide the means for permitting it to be raised in the cylindrical opening 5. Furthermore, the shape of the cross section of the pin, the cylindrical opening through which it moves, and the opening in the tongue, is not critical. A pin having a square, oblong, or any other cross section would also be effective.
The ferrule may be enclosed in a sheath 9 as in FIGS. 1, 2, 3 and 4, or arranged without a sheath as in FIGS. 5 and 6. Where the sheath has been used as in the first four figures, we have shown this sheath 9 in combination with the forepart 11 of a housing 12, said forepart carrying the elongated opening which serves to guide the tongue 2 into the slot of the ferrule.
Referring now more particularly to FIG. 1, ferrule 1 slips into sheath 9 with the cylindrical opening of the ferrule coinciding with an opening 13 of the sheath, and slot 4 of the ferrule coinciding with elongated openings 14 of the sheath.
Spring supporting member 15 is pressed over sheath 9 and fixed thereto. This may be accomplished by a pin, screws or rivets 16. Extending arms 17 provide a support for ejection springs 18, and preferably these have cylindrical depressions or short projections to provide seats for the ends of springs 18.
Tongue ejector 19 is placed in slot 4 of the ferrule, with arms 21 extending beyond both the ferrule 1 and sheath 9. The slot 4 extends far enough to the rear to accommodate both the tongue ejector 19 and the fully inserted tongue 2, behind it. Arms 21 of the tongue ejector, as with those of the spring support member 15, preferably have shallow cylindrical indentations 20 for seating springs 18 which are now positioned between arms 17 and 21 to thus bias the tongue ejector 19 toward the front of the buckle. The forepart of the housing serves as the forward stop for the biased tongue ejector 19.
Flat spring 22 is attached to the top of pin 7 with rivet 23 or other means. The pin 7 is placed in cylindrical opening 5, and the bifurcated end 24 of the push button member 25 is slipped into that portion of the pin of reduced diameter. The fulcrum 26 of the push button member 25 is positioned over the raised pivot edge 27 of the sheath 9.
Saddle-shaped flat spring 28 is attached to the sheath with rivet 29 or other means, and serves to bias the push button 25 upward.
When the components are assembled in housing 12, push button 25 is accessible through opening 31 of the housing. In the embodiment shown in FIG. 1, opening 32 of the housing is engaged by recessed groove 33 of the sheath. A cable or other restraint can be permanently crimped into opening 5 of the ferrule.
The action of the buckle can better be understood by examining FIGS. 2 and 3. In FIG. 2, tongue 2 is inserted in the slot of the ferrule, and pin 2 extends through the opening in the tongue, locking it securely in place. The tongue ejector 19 has been forced back against its bias by the insertion of the tongue. The extended arms of the spring support 17 and of the ejector 21 are shown in phantom, and the arrows between them represent the compressed ejecting springs 18.
In FIG. 3, push button 25 has been depressed against the bias of flat spring 28 beneath it. Rocking back on fulcrum 26, the bifurcated end 24 of the push button member has raised pin 7 against the bias of flat spring 22 acting against the inner surface of the housing. The pin has been extracted from the opening in the tongue whereupon tongue ejector 19 has ejected tongue 2 as a result of the extension of the tongue ejector springs 18. The amount of this spring extension is indicated by the arrows between the arms of the spring support member 15 and the ejector 19.
When the pin 7 was released and the ejector shot forward, it came to rest over the cylindrical opening 5, thus when the push button was released, the ejector supported the pin, keeping it out of the slot and holding it in readiness for the next tongue insertion.
When the tongue is next inserted it forces back the tongue ejector 19 against the bias of springs 18, and as soon as the opening 6 in the tongue 2 comes in line with pin 7, it drops through the opening, biased thereto by flat spring 22, thus latching the tongue securely within the buckle.
The parts shown in FIG. 4 differ only slightly from those of FIGS. 1, 2 and 3. Bifurcated end 24 of the push button member slips beneath the head of cylindrical pin 7. The push button member has extended legs 31 journaled on projections 32 on opposite sides of the sheath. These projections can be shafts extending part way into the ferrule, or a single shaft passing through the ferrule to extend beyond the sides of the sheath on either side.
The upward bias of the push button and the downward bias of the pin are here supplied by a single trifurcated flat spring 33, the central tine of which supplies the downward bias to the pin. In FIG. 4, the bifurcated portion of the push button member and the flat trifurcated spring are repeated in inserts for clarity.
In FIG. 5, a sliding push button 34 is employed to extract pin 7 from the tongue. The pin is shown as cylindrical throughout its length. Near the top it has two openings or a single through opening to accommodate the ends of springs 35. These springs supply the downward bias to the pin. The other ends of these springs are fixed within the housing.
Wedges 36 are positioned on either side of the pin. At the foot of each wedge there is a raised ridge 42 which limits the outward movement of the sliding push button. When the sliding push button is pressed, the ends 35 of the springs are caused to ride up the advancing sloping surfaces of the wedges, raising the pin to which they are attached. As before, when the tongue is ejected, the tongue ejector comes to rest in the slot beneath the cylindrical opening, so that the pin is restrained above the slot until the tongue is again inserted.
An exploded view of the ferrule 1 including the tongue ejector 19 and the ejection spring 18 is shown. In this embodiment the slot is below the axis of the ferrule, and a concentric cylindrical opening 37 extends within the ferrule for the accommodation of a single coiled ejection spring 18. For that portion of the cylindrical opening common with the slot, the lower surface of the slot is substantially tangential with the cylindrical opening 37 as shown. A small protrusion 38 extending from the rear of the tongue ejector cooperates with the end of the ejector spring 18, while the arms 39 extending from the tongue ejector beyond the sides of the ferrule, contact the inner surface of the front face of the buckle when fully extended, thus providing a stop at the end of its forward travel at which point it is directly beneath the pin. The notches 41 in the extended arms permit a bit more rearward travel in that they provide space for that bit of spring 35 with which each side comes in contact.
Ridges 43 of the sliding push button slideably cooperate with corresponding grooves within the housing, and preferably spring bias is provided to maintain the sliding push button in its usual extended position. Such bias is optional, and is not shown.
The arrangement of this embodiment can be better understood by reference to FIG. 6, a half-section in elevation. Tongue 2 is shown inserted and latched into place, for pin 7 extends through the opening in the tongue. The pin is biased downwardly by springs 35. The tongue is restraining ejector 19 against the bias of spring 18. The wedges 36 are shown in phantom. The housing 12 differs from that of FIG. 1 through 4, being adapted for the use of sliding push button 34. It can be seen that pressure on the sliding push button containing wedges 36, will extract the pin from the tongue. When this occurs, tongue ejector 19 will eject the tongue and simultaneously position itself beneath the pin, holding it above the slot against its bias. It will remain there until displaced by an inserted tongue, then, when the opening in the tongue advances to a point beneath the biased pin, it will drop into latching engagement with the tongue.
While we have described preferred embodiments of our invention, it will be understood that various modifications can be made in the buckle and tongue combination described without departing from the spirit of this invention or the scope of the following claims.
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A safety buckle and tongue in combination wherein pressure on the tongue release push button is employed at a mechanical advantage, hence the buckle is unlatched with a minimum of effort even under conditions of stress. A ferrule provides a continuous link between the members of the restraint system to be connected, providing great strength and reliability.
A pin, biased downwardly, latches the inserted tongue securely by entering an opening in the tongue. In inserting the tongue, an ejection member within the slot is forced back against its bias. When the pin is extracted from the tongue by the pressing of a push button, the tongue is ejected and the ejection member comes to rest directly beneath the pin, restraining it above the slot until displaced by the reinsertion of the tongue.
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This invention relates to a system and a method for tracking marked documents, or computer-readable files of any type, within a network computer system.
Network computer systems allow the easy transfer of files from one user to another, with clear benefits to the organizations operating such computer systems. However, network computer systems can also be used to transfer documents to unauthorized or unintended recipients.
Systems have been proposed in order to deal with this problem.
For example, WO 01/50691 describes a controlled secure email delivery mechanism whereby data is held with a message, and that data is used by the mail reading program to limit the onward transmission of that message. However, this has the disadvantage that, even if the email client limits printing or forwarding of the message, there is apparently nothing to prevent the user from copying the text and pasting it into a new message.
EP 08940194 describes a way of limiting distribution of documents that have been paid for, by embedding payment information within the data and ensuring that any program that accesses this data checks the payment authorization. One potential disadvantage with this type of system is that, since the protection data is embedded within the data, it can potentially be tampered with by the recipient. In the case of EP 08940194, strong cryptography is used to ensure that the protection data held within the document cannot be tampered with. However, the requirement to use strong cryptography in this way is a disadvantage in itself.
Systems also exist which allow a computer to identify particular types of electronic file, such as viruses and spam email, and restrict the user's ability to process those files. However, those limits on the user's ability are not set by the originators of the files, but are imposed subsequently, for example by the writer of an anti-virus program.
For example, U.S. Pat. No. 5,319,776 describes a system for detecting viruses in computer data streams. Specifically, data in transit between a source computer and a destination computer is tested against search strings representing the signatures of multiple known computer viruses. When a virus is detected, the data is prevented from remaining on the destination computer storage medium.
According to a first aspect of the present invention, there is provided a method of controlling data processing, the method comprising:
a) receiving user-specific originator preferences relating to data; and storing said originator preferences and a representation of the data in a database; b) allowing access to said data by other users; and c) in response to a request by any user for processing of a file: identifying whether the file contains data identical to or sufficiently similar to said data; and, if so: determining the identity of the requesting user; determining from the database whether said requested processing is consistent with any stored originator preferences relating to the requesting user; and
permitting the requested processing only if said processing is consistent with the stored originator preferences.
According to a second aspect of the present invention, there is provided a client computer device, comprising:
means for requesting originator preferences relating to a created file; means for forming an indication of a content of said file; and means for sending receiving originator preferences, in association with said indication of the content of said file, to a database for storage.
According to a third aspect of the present invention, there is provided a computer program product, for use on a client computer device connected to a computer network, the computer program product containing code for causing said device to:
request originator preferences relating to a created file; identify an originator of the file; form an indication of a content of said file; and send received originator preferences, in association with said indication of the content of the file, over said computer network to a network server.
According to a fourth aspect of the present invention, there is provided a client computer device, comprising:
means for receiving a request for processing of a file; means for forming an indication of a content of the file; means for sending the indication of the content of the file, and an identity of a user of the client computer device, to a server device; and means for performing the requested processing only if permitted by said server.
According to a fifth aspect of the present invention, there is provided a server computer device, comprising:
means for receiving originator preferences relating to a first file, in association with an indication of a content of said first file; means for receiving notification from a user of a request for processing of a second file, in association with an indication of a content of said second file, and an indication of the identity of the user; means for determining from said indications whether said contents of said first and second files are identical or sufficiently similar; means for retrieving received originator preferences, if said contents of said first and second files are identical or sufficiently similar; and means for permitting the requested processing of said second file only if it is consistent with any retrieved received originator preferences relating to that user.
Thus, the storage of user-specific originator preferences on a server means that the users are not able to override the originator preferences by tampering with received documents.
FIG. 1 is a block schematic diagram, showing a computer system in accordance with an aspect of the present invention.
FIG. 2 is a flow chart, showing steps performed in a client device, and in a server, of the computer system of FIG. 1 , at a first stage in a process in accordance with an aspect of the present invention.
FIG. 3 is a flow chart, showing steps performed in a client device, and in a server, of the computer system of FIG. 1 , at a second stage in a process in accordance with an aspect of the present invention.
FIG. 4 illustrates a user interface presented to a user in operation of the system in accordance with the invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 is a schematic diagram, showing a computer system 10 . The system 10 includes two client computers 12 , 14 , connected over a local area network (LAN) 16 , which also includes a server computer 18 . It will be appreciated that the network 10 may well have more than two client computers connected to it. However, the invention can be sufficiently described with reference to a network containing two client computers.
The first client computer 12 can run application software 20 , and has an associated document management agent (DMA) 22 . The second client computer 14 can run application software 24 , and has an associated document management agent (DMA) 26 . The server 18 runs tracking software 28 , and has access to a database 30 . The database 30 is shown as part of the server 18 , but can instead be provided on a separate device accessible from the server 18 . The functionality of the server 18 , as described below, can be provided on a network server machine, or on a separate machine only dealing with this functionality. One or more such server can be used to provide the required functionality.
In a corporate or other network environment, the system administrator can take steps to ensure that a client computer will not operate if the document management agents 22 , 26 are removed or disabled.
The invention is described herein with reference to an example in which the application software 20 , 24 running on the client computers 12 , 14 , comprises an email program. However, the invention is applicable to all operations in which files can be transferred from one user to another, or can be made available to multiple users.
FIG. 2 is a flow chart, illustrating a first phase of the operation of the system 10 . In step 40 of the process, a document is created by a first originating user, and a document movement request is made in the application software 20 on the client computer 12 . Although the term “document” is used herein, it will be appreciated that the invention is applicable to any form of computer file, such as an email message, an email attachment, a word processing document, a spreadsheet, or a presentation. Further, although the invention is specifically described with reference to its use in an email program, the document movement request may be made in many types of software.
Further, while FIG. 1 shows a situation in which the document management agents 22 , 26 are located in their respective client devices 12 , 14 , in an alternative embodiment of the invention, the document management agents may be located in the servers that are accessible by the user computers. For example, in order to be able to send email, a user computer must be connected to an email server computer, and the functionality of the document management agents 22 , 26 , as described in more detail below, can instead be located in the network email server or servers, as well as in other servers which handle similar requests, such as web servers and file transfer protocol servers.
When the document has been created, and the document movement request has been received, the document management agent software 22 asks the originating user to confirm whether any tracking requirements are to be associated with the document. These originator preferences may for example include a requirement that the document should not be sent to recipients outside a specified group of recipients, or that it should not be sent outside the organisation running the LAN 16 , or that it should be tracked whenever it is moved, or various other options. In addition, the originator preferences may be time dependent. That is, the originator preferences may specify that certain actions are permissible only before a certain time has expired, or only after a certain time has expired, or only within a defined time window.
Although, in this situation, the originator preferences are associated with the document at the time that the document is created, it should be noted that the originator preferences may be associated with the document at a later time, either by the user that created the document, or by another user who had access to the document. In the latter case, the originator preferences may apply only to copies derived from the user who added the originator preferences.
If the originator sets any such requirements, then, in step 44 , the document management agent software 22 forms a digest of the document. The digest is a version of the document, which will allow it to be recognized later. The digest could be a complete copy of the document, or could be something derived from the document. Preferably, the digest is formed in such a way that recognition will still be possible, even though the document may have been altered.
At the simplest level, the digest is simply the original document stored in its entirety. In this case, the document can be recognized later by applying conventional similarity tests.
However, from the point of view of reducing the storage requirements, it is advantageous to form a digest that contains less data than the original document. For example, a hash can be formed according to a known technique. If the hash space is large enough, then the possibility of producing two identical hashes from non-identical documents can be set to effectively zero.
An alternative would be to use Bayesian techniques to identify the topmost fifty or so relevant words in the source document and then use these as the digest or a part of the digest. For example, the digest could include both these most relevant words and some other data such as the entire document. Then, when testing a document for recognition, a full comparison for similarity would only be performed on those documents having the same relevant word list.
A further alternative would be to use the technique suggested by Paul Rubin in a document currently available on the Internet at http://groups.google.co.uk/groups?q=paul+rubin&hl=en&lr=lang_en&group=alt.current-events.net-abuse.*&safe=off&selm=phrD4A6lp.LFA%40netcom.com&rnum=6, where a set of overlapping hashes are created for every 15-byte sequence in the document, and then the majority of these are discarded leaving, say 100 values. These are stored in a sorted list which can be used to determine whether the documents contain terms in common.
Once the digest has been formed, in step 44 , it is sent, together with the tracking requirements received in step 42 , to the server 18 , and these are stored in the database 30 , in step 50 of the process.
In this illustrated embodiment of the invention, the original document is also sent to the server 18 for storage in the database 30 .
FIG. 3 is a flow chart, illustrating a second phase of the operation of the system 10 , once the document has been made available to a second, recipient, user. Thus, in the illustrated embodiment of the invention, the document is sent to the second user by email. In other embodiments of the invention, or in other uses of this embodiment, the document may be made available on a file server for downloading by the second user, or the second user may be enabled to access the document in any other way.
Although this description assumes that a particular document, to which originator preferences have been applied, has been made available to the recipient, the process is applied whenever a user performs any document processing, and the process includes determining whether the document processing relates to a document that has previously had originator preferences stored in association with it.
In step 60 of the process, a document processing request is made in the application software 24 on the client computer 14 . For example, the document processing request may be a request from the user to open a specified document, or to modify the specified document, to save the document to a specific location on the computer system 10 , or to save the document to a removable storage device, or to forward an email to a specific email address.
In step 62 , the document management agent software 26 forms a digest of the document, using the digest formation technique in use in the system, for example selected from the techniques discussed above.
In step 64 , the client computer 14 notifies the server 18 of the digest formed in step 62 , the identity of the recipient user, and the form of document processing requested.
In step 66 , the server 18 tests whether the document processing request complies with any previously set originator preferences. As a first stage of step 66 , the server 18 tests from the digest formed in step 62 whether the document corresponds to any of the documents for which originator preferences have been stored in the database 30 .
As mentioned above, in preferred implementations of the invention, the server 18 is able to test not just whether the document is exactly the same any of the documents for which originator preferences have been stored in the database 30 , but whether it is a modified version of any of the documents for which originator preferences have been stored in the database 30 . Techniques exist for testing for this similarity. In addition, some of this testing can make use of knowledge of document structures. For example, when an email message is forwarded, information about who originally sent it is included, and line markers such as “greater than” signs (>>) are inserted at the start of each line. These can be excluded before the digest is created in step 62 , as can any text added by the forwarder before the forwarded text.
As a second stage of step 66 , if it is found that the document corresponds to one or more of the documents for which originator preferences have been stored in the database 30 , the server 18 tests whether the document processing request complies with the preferences set for that recipient user.
For example, the originator may have set a preference that the document may be forwarded only to recipients within the originator's and recipient's company, or immediate workgroup, or may have set a preference that the document may be stored only to some locations on the network and may not be saved to a removable storage device.
In addition, as mentioned above, the preference may state that certain actions are permissible only at certain times.
Based on the stored preferences, the server 18 therefore determines whether the document processing request complies with those preferences and, in step 68 , it notifies the client device accordingly.
In step 70 , the client device 12 acts in accordance with the notification received from the server 18 . For example, the client device may be able to comply with the document processing request, or it may have to decline the request. Further, in accordance with a preference set by the originator of the document, the client device 14 may notify the originator client device 12 as to any operations performed on the document.
As a result of this, the originator is therefore able to check the operations that have been performed on the documents for which such notifications have been requested.
There is therefore described a system in which it can be determined whether a document processing request complies with any stored preferences relating to the document. Moreover, in particularly advantageous embodiments, the system is able to determine if the document is simply a modified version of a document for which preferences have been stored and, if so, is still able to ensure compliance with those preferences.
These determinations can be made in the server 18 , or in the recipient's client computer 14 , or can be made between the server 18 and the recipient's client computer 14 .
For example, the determinations can be made in the server 18 if the client computer 14 notifies the server 18 of the digest formed in step 62 , the identity of the recipient user, and the form of document processing requested. In that case, the server 18 can determine if the digest sufficiently closely matches any of the digests of documents which have associated stored preferences, and, if so, can then determine whether the document processing request complies with the preferences set for that recipient user.
The final determination can be made in the recipient's client computer 14 if, in response to a notification of the name of the document, the server 18 informs the recipient's client computer 14 of the relevant stored preferences and the recipient's client computer 14 can then determine whether the document processing request complies with the preferences set for that recipient user.
The decision making can be shared between the server 18 and the recipient's client computer 14 if, for example, recipient's client computer 14 stores the digests of documents which have associated stored preferences, and then sends the original document to the server 18 , together with information about the identity of the recipient user, and the form of document processing requested, if an initial comparison of the digest suggests that the document may in fact be a modified version of a document which has associated stored preferences. If so, the server 18 can then determine, based on a conventional similarity test, whether that is true and, if so, whether the document processing request complies with the relevant preferences.
FIG. 4 illustrates a user interface, by means of which the originator is able to check such operations.
In FIG. 4 , the user interface 80 displays a list 82 of documents that have had tracking information applied to them, and a similar list 84 of emails. In the list 82 of documents, the document “Suggestion.txt” 86 is highlighted, indicating that the user has selected this document for more detailed information. On the right hand side 88 of the interface 80 , the system then displays (at 90 ) the originator preference that has been set, and (at 92 ) the history of where the document has been sent.
Thus, we can see that the document was created by the user FS, and sent by email to the user JD. The user JD saved a copy of the document on her machine, with the asterisk 94 indicating that the saved copy is more or less the same as the original, but has been slightly altered. The user JD sent the slightly altered copy to another user HJ. However, as there is as yet no copy of the document on the user HJ's machine, we can assume that the user HJ has not yet read his email.
There is therefore described a system which allows a user to track movement of a document around an organization, as well as possibly restricting the recipients' ability to process the document. The tracking of the document is useful because it allows a user to discover who has received a copy of a document, for example so that, when an updated version of the document is produced, that updated version can conveniently be sent to all of the recipients.
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When data is stored on a computer, or subsequently, originator preferences relating to the data are stored in a database, for example in a network. When another user subsequently makes a request for processing of the received data, or a modified copy of the data, it is determined whether the requested processing is consistent with any stored originator preferences, and the requested processing is permitted only if it is consistent with the stored originator preferences. The preferences may relate to saving, copying or retransmitting the data. The originator may be notified of any processing operations that are carried out.
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This application is a continuation-in-part of the U.S. patent application for "Process for Preparing 10-Deazaaminopterins and 5,10- and 8,10-Dideazaaminopterins from Pteroic Dicarboxylic Acid Diesters" Ser. No. 08/028,431 pending filed on Mar. 9, 1993 and of the U.S. patent application for "Heteroaroyl-10-Deazaaminopterins and 5,10-Dideazaaminopterins for Treatment of Inflammation" Ser. No. 08/008,919 pending filed on Jan. 26, 1993 and of the U.S. patent application for "Heteroaroyl-10-deazaaminopterins for Treatment of Inflammation" Ser. No. 07/938,105 filed on Aug. 31, 1992 now abandoned and of the U.S. patent application for "10-Alkenyl and 10-Alkynyl-10-Deazaaminopterins," Ser. No. 07/845,407 filed on Mar. 3, 1992, now abandoned and of the U.S. patent application for "5-Deazaaminopterins and 5,10-Dideazaaminopterins for Treatment of Inflammation, Ser.No. 07/875,779 filed on Apr. 29, 1992, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The current invention concerns novel antiinflammatory and antineoplastic 10-deazaaminopterin compounds. In particular, the invention concerns heteroaroyl-10-deazaaminopterins and 10-alkenyl or 10-alkynyl-10-deazaaminopterins having pronounced antiinflammatory activity, antileukemic and antitumorigenic activity, as well as a method for treatment of inflammatory diseases, leukemia and tumors. Pharmaceutical compositions containing these heteroaroyl-10-deazaaminopterin compounds are also disclosed. The invention further concerns a process for preparation of these compounds.
BACKGROUND OF THE INVENTION AND RELATED DISCLOSURES
Rheumatoid arthritis, malignant tumors and leukemia are severely debilitating diseases which are often fatal, as in cases of leukemia and malignant growths. Drugs which are currently available and used for treatment of these diseases typically have unpleasant secondary symptoms or are highly toxic.
Rheumatoid arthritis is one of a number of forms of proliferative disease, and the development of drugs for amelioration or curing the disease has occupied the attention of research organizations for many years, until most recently without appreciable success.
Rheumatoid arthritis is an inflammation of the joints arising from infectious, metabolic, or constitutional causes, usually of unknown origin. In its advanced stage it is debilitating, as it can result in serious restriction of movement and even invalidism. Since rheumatoid arthritis is a common disease that affects 2-3 million people in the United States alone, it poses a serious health problem. With disease progression, a substantial proportion of affected individuals develops erosive joint disease and despite therapies including disease-modifying antirheumatic drugs such as gold complexes, penicillamine, antimalarials, and methotrexate often require surgical joint replacement. In some patients with intractable rheumatoid arthritis, administration of immunosuppressive agents including azathioprine, methotrexate, cyclophosphamide, and combinations of these drugs have been proven beneficial. However, the actual or potential side effects of some of these drugs, including bone marrow toxicity and neoplasia, have limited the frequency and the dose at which they can be administered.
Leukemia is an acute or chronic disease of unknown cause which is characterized by malignant neoplasm of the blood forming tissues in man and other warm-blooded animals. It is characterized by an abnormal increase in the number of immature leukocytes in the tissues of the body and in the circulating blood. The disease apparently affects the blood-forming organs, and is classified according to the type of leukocyte that is being proliferated abnormally. The disease is one of a number of forms of neoplastic disease, and the development of drugs for amelioration or curing the disease has been of great interest. Today, many forms of leukemia can be effectively treated with drugs. In the case of combination chemotherapy with acute lymphocytic leukemia in children, a large percentage, (50-60%) of five year survivals are obtained, and the disease is now classified as curable.
Malignant tumors result from a cellular malignancy whose unique characteristics--loss of normal cellular controls and regulations--results in unregulated growth, lack of differentiation, and ability to invade local tissues and metastasize.
There is no effective treatment of malignant growths aside from radical surgery. Once, however, the tumor metastasizes, the only therapies which are somewhat effective are radio and chemotherapy. Both these therapies have severe side-effects which make them very unpleasant.
It would thus be extremely useful to provide therapies for rheumatoid arthritis, leukemia and malignant tumors with drugs which would be less toxic and still be effective in treatment of these diseases.
The antifolic acid drug, methotrexate, has been used as an antitumor agent since 1955. Its cytotoxic action in tumors is related to its ability to inhibit, essentially irreversibly, the key enzyme, dihydrofolate reductase, required for biosynthesis of tetrahydrofolic acid. Tetrahydrofolate is a vital component in one-carbon metabolism in cells, being required for biosynthesis of purine and pyrimidine nucleosides of the DNA and RNA. The drug is a powerful cytotoxic agent whose principal toxicities occur with liver, kidney, and mucosal tissue. Liver toxicity is the paramount concern for use in chronic therapy in a disease such as arthritis.
The ability of methotrexate to affect the inflammatory conditions of rheumatoid arthritis may be linked to its cytotoxic behavior. This may be in the nature of immune suppression and could involve attack on inflammatory phagocytic cells such as macrophages or neutrophils and T-helper cells in the synovial region. Very few methotrexate analogues have been evaluated against arthritis in animals, and there is no clear indication whether the antiarthritic properties are directly proportional to cytotoxicity. Studies published in Chem. Biol. Pteridines, 847 (1986) DeGuyter, Berlin, showed that adjuvant arthritis and streptococcal cell wall arthritis in rats responded to doses of methotrexate which were in good correlation to those used in man for treatment of rheumatoid arthritis and that timing and dosage were both important for reduction of inflammation. Both methotrexate and aminopterin were found to inhibit inflammation, but other antifolate compounds that did not possess a 2,4-diaminopyrimidine unit or a benzoylglutamate side chain were ineffective.
In 1974, J. Med. Chem,, 17:552, reported the synthesis and antifolate activity of 10-deazaaminopterin. The antimicrobial and antitumor activities of the powerful dihydrofolic reductase inhibitors aminopterin and its N-10 methyl derivative, methotrexate, are well known, and numerous analogues have been made to further improve the potency, cell penetration and toxicity properties of these compounds.
U.S. Patent No. 4,369,319, issued Jan. 19, 1983, discloses 10-deazaaminopterin compounds having the following structure: ##STR1## wherein R 1 and R 2 are both hydrogen or alkyl having from one to about eight, preferably one or two carbon atoms, or when only one of R 1 and R 2 is alkyl, and the other is hydrogen.
These alkyl derivatives were found active against leukemia as well as against other malignancies, including ascitic tumors, which can be ameliorated in warm-blooded lower animals by the administration of 10-deazaaminopterin. The use of deazaaminopterin as antirheumaticum is described in the use U.S. Pat. No. 5,030,634. The sole compound described in the '634 patent is identical to the compound, described in U.S. Pat. No. 4,369,319, wherein both R 1 and R 2 are hydrogens.
Other derivatives of methotrexate, namely pyrido[2,3-] pyrimidines disclosed in U.S. patent No. 5,026,851 were found to be active against neoplastic growth. The process to prepare these compounds is disclosed in the U.S. Pat. No. 4,988,813.
It is therefore a primary object of this invention to provide an effective treatment for inflammatory diseases, such as rheumatoid arthritis as well as an effective drug for inhibition of malignant neoplasms of the blood forming tissues and for inhibition of growth of malignant tumors with compounds, which exhibit relatively low toxicity compared to current treatments.
All references cited herein and in the following text are hereby incorporated by reference in their entirety.
SUMMARY
One aspect of the current invention is heteroaroyl-10-deazaaminopterin compounds of formula (I) ##STR2## wherein X is selected from ##STR3## and R is hydrogen or alkyl, alkenyl, or alkynyl having from one to about eight carbon atoms, preferably from one to one carbon atoms for alkyl and three to five carbon atoms for alkenyl and alkynyl.
Another aspect of the current invention is a method for treatment of rheumatoid arthritis by administering to a patient in need of such treatment an effective amount of the compound of formula (I) or its pharmaceutically acceptable salt.
Still another aspect of the current invention is a method for inhibition of malignant neoplastic growth of the blood forming tissue or malignant tumor growth of other tissues by administering to a patient in need of such treatment an effective amount of the compound of formula (I) or its pharmaceutically acceptable salt.
Still another aspect of the current invention is 10-alkenyl-10-deazaaminopterin and 10-alkynyl-10deazaaminopterin compound of formula (II) ##STR4## wherein R 1 and R 2 are selected from the group consisting of hydrogen, alkynyl and alkenyl having from one to about eight, preferably three to five carbon atoms.
Another aspect of the current invention is a method for treatment of rheumatoid arthritis by administering to a patient in need of such treatment an effective amount of the compound of formula (II) or its pharmaceutically acceptable salt.
Still another aspect of the current invention is a method for inhibition of malignant neoplastic growth of the blood forming tissue or malignant tumor growth of other tissues by administering to a patient in need of such treatment an effective amount of the compound of formula (II) or its pharmaceutically acceptable salt.
Still yet another aspect of the current invention is a process for preparing compounds of formula (I).
The final aspect of the current invention is a process for preparing compounds of formula (II).
DETAILED DESCRIPTION OF THE INVENTION
The current invention concerns novel 10-deazaaminopterin compounds which are nontrivial analogues of methotrexate and which are either as effective or more effective in treatment of rheumatoid arthritis or for inhibition of malignant neoplastic growth.
The invention also provides a method of treating arthritis and other proliferative diseases, as well as inhibiting malignant neoplastic growth, which method comprises administering to a warm-blooded animal having an inflammation of the joints or other evidence of the disease or suffering from leukemia or tumorigenic growth, a therapeutic nontoxic amount of a 10-deazaaminopterin compound or a pharmaceutically acceptable salt thereof. These salts are formed with one or more free NH2 groups and/or COOH groups of the 10-deazaaminopterin compound.
I. Heteroaroyl-10-Deazaaminopterins
In accordance with the present invention, heteroaroyl-10-deazaaminopterins are compounds of formula I ##STR5## wherein X is one of ##STR6##
and R is hydrogen or alkyl, alkenyl, or alkynyl having from one to about eight carbon atoms, preferably from one to three carbon atoms for alkyl and three to five carbon atoms for alkenyl and alkynyl.
Exemplary alkyl substituent includes methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, iso-amyl, sec-amyl, tert-amyl, hexyl, iso-hexyl, heptyl, iso-heptyl, octyl, iso-octyl, 2-ethyl hexyl, and tert-octyl.
Exemplary alkenyl substituent includes allyl, crotyl (2-butenyl), 2-pentenyl, 2-pentenyl, 2-hexenyl, 2-hexenyl, 3-isopropenyl, 3-isobutenyl, and 2-octenyl.
Exemplary alkynyl substituent includes propargyl, 2-butynyl, 3-butynyl, 2-pentynyl, 2-hexynyl, and 2-octynyl.
A subclass of pyridyl compounds within the scope of the invention is defined by formula IA ##STR7## wherein Y is selected from ##STR8## and R is hydrogen or alkyl, alkenyl, or alkynyl having from one to about eight carbon atoms, preferably from one to three carbon atoms for alkyl and three to five carbon atoms for alkenyl and alkynyl.
One subclass of thienyl compounds and thienyl analogues within the scope of the invention is defined by formula IB ##STR9## wherein Y is selected from ##STR10##
and R is hydrogen or alkyl, alkenyl, or alkynyl having from one to about eight carbon atoms, preferably from one to three carbon atoms for alkyl and three to five carbon atoms for alkenyl and alkynyl.
Exemplary heteroaroyl-10-deazaaminopterin compounds falling within the scope of the formula IA and IB are shown in the Table 1.
TABLE 1______________________________________Compound # R.sub.1 X______________________________________1 2 H C.sub.2 H.sub.5 ##STR11##3 4 H C.sub.2 H.sub.5 ##STR12##5 6 H C.sub.2 H.sub.5 ##STR13##7 8 H C.sub.2 H.sub.5 ##STR14##9 10 H C.sub.2 H.sub.5 ##STR15##11 CH.sub.3 ##STR16##12 CH.sub.3 ##STR17##13 CH.sub.3 ##STR18##14 CH.sub.3 ##STR19##15 CH.sub.3 ##STR20##16 17 18 19 20 21 22 C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 CH.sub.2CHCH .sub.2 CHCCH.sub.2 C.sub.5 H.sub.11 C.sub.8 H.sub.17 ##STR21##23 24 25 26 27 28 29 C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 CH.sub.2CHCH .sub.2 CHCCH.sub.2 C.sub.5 H.sub.11 C.sub.8 H.sub.17 ##STR22##30 31 32 33 34 35 36 C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 CH.sub.2CHCH .sub.2 CHCCH.sub.2 C.sub.5 H.sub.11 C.sub.8 H.sub.17 ##STR23##37 38 39 40 41 42 43 C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 CH.sub.2CHCH .sub.2 CHCCH.sub.2 C.sub.5 H.sub.11 C.sub.8 H.sub.17 ##STR24##44 45 46 47 48 49 50 C.sub.3 H.sub.7 i-C.sub.3 H.sub.7 n-C.sub.4 H.sub.9 CH.sub.2CHCH .sub.2 CHCCH.sub.2 C.sub.5 H.sub.11 C.sub.8 H.sub.17 ##STR25##______________________________________
II. Preparation of Heteroaroyl-10-Deazaaminopterins
Heteroaroyl-10-deazaaminopterins are prepared by processes described in following reaction schemes 1-4.
The compounds of Formula IA, wherein X is ##STR26## are synthesized by the procedure illustrated in Reaction Scheme 1. ##STR27##
Reaction Scheme 2 illustratesoa preparation of pyridyl compounds wherein X is ##STR28## by substituting a starting compound in the Reaction Scheme 1 with compound of the formula ##STR29## used as a starting compound in the Reaction Scheme 2. The synthetic process illustrated in Reaction Scheme 2 differs from procedures illustrated in Reaction Scheme 1 at intermediate steps II-2 to II-5 because it is necessary to use the pyridine carboxylate protected as an ester to prevent its decarboxylation in the step II-5 to II-6 ##STR30##
The following procedure illustrated in Reaction Scheme 3 is used to prepare thiophene analogues of compound of formula I. ##STR31##
The same procedure suitable to prepare analogues of 10-deazaaminopterins wherein X is thiophene, illustrated in the Reaction Scheme 3, is used to prepare thiazole or thiadiazole analogues of 10-deazaaminopterins of formula I.
An alternative procedure shown in Reaction Scheme 3a can be used to substitute a process for preparation of thiophene dimethyl ester II 5a in Reaction Scheme 3. ##STR32##
Heteroaroyl-10-deazaaminopterins wherein the substituent Y is 2-pyridyl is prepared by treating diisopropylamine dissolved in dry tetrahydrofuran with n-butyl lithium dissolved in an organic solvent such as hexane, pentane, heptane, or octane, and stirred at 0° C. for about 1 hour. The lithium diisopropyl amide solution is added dropwise over 15°90 min to a -25° C. mixture of 6-methylnicotinic acid and hexamethylphosphorous triamide in dry tetrahydrofuran. The temperature of the red solution is allowed to rise to about 0° C. with continuous stirring for 2 h. Carbon dioxide is bubbled through the 0° C. solution. The mixture is allowed to rise to room temperature and is stirred for another 8-24 hours. Filtration gives a solid which is suspended in an alcohol, preferably in methanol, the mixture is cooled to about 0° C. and acidified with preferably methanolic hydrochloric acid. After stirring for 1-5 days, preferably for 3 days, the mixture is concentrated and partitioned between organic and aqueous solvent, preferably between ether and saturated sodium bicarbonate. The organic layer is washed, rinsed and dried to yield product compound I-1, namely 5-carboxymethoxy-2-pyridylacetic acid methyl ester.
To a suspension of sodium hydride in dry dimethyl formamide is added a solution of I-1 in an organic solvent such as dry dimethyl formamide. The mixture is stirred at around 0° C. for 30-90 minutes, preferably for 60 minute, then cooled to about -30° C. A solution of ethyl iodide in dry dimethyl formamide is added dropwise, maintaining a reaction temperature of about -25° C. The mixture is then stirred for 1-4 hours, preferably for 2 hours at room temperature. The reaction is neutralized to about pH 8 by adding solid carbon dioxide, and the product is then concentrated under high vacuum. The residue is partitioned between ether and water, the organic layer is washed with preferably mixture of 10% sodium bicarbonate, 10% sodium bisulfite, and water. The organic layer is dried and concentrated to a pale brown oil, α-ethyl-5-carbomethoxy-2-pyridylacetic acid methyl ester (I-2).
A solution of I-1 dissolved in dry dimethyl formamide is added to a suspension of sodium hydride dissolved in dry dimethyl formamide. The mixture is stirred at around 0° C. for 10-60 minutes, preferably for 30 min, then cooled to about -30° C. A solution of 2,4-diamino-6-bromomethylpteridine hydrobromide dissolved in dry dimethyl formamide is slowly added dropwise over about 40 min. The reaction is stirred for about 2.5 h at 5°-20° preferably at 10° C., and the pH is adjusted to pH 8 by adding dry ice. The mixture is concentrated under high vacuum to give a solid, 3-(2,4-diaminopyrimido[4,5-b]pyrazin-6-yl)-2-(3-carbomethoxypyrid-6-yl)-propionic acid methyl ester (I3a).
A solution of the ester I-3a dissolved in an alcohol, such as 2-methoxyethanol, water, and a base such as 10% sodium hydroxide is stirred for 1-4 hours, preferably for 2.5 hours and then diluted with water. The pH of the reaction is adjusted to pH 6 with an acid, preferably with glacial acetic acid. The cream-colored precipitate is collected, and dried to yield the dicarboxylic acid I-4a.
A mixture of the dicarboxylic acid I-4a in dry argon-purged dimethyl sulfoxide is heated to 90-130, preferably to 110° C. for 15-60 minutes, preferably for 25 min, then concentrated under high vacuum. The residue is suspended in an aqueous solvent, preferably in water and sufficient base such as ammonium hydroxide is added to produce a solution. The solution is adjusted to about pH 5 by dropwise addition of an acid, such as glacial acetic acid, to yield the product β-(2,4-diamino-[4,5-β]pyrazin-6-yl)-6-ethylnicotinic acid (I-5a).
A mixture of the carboxylic acid (I-5a) dissolved in an organic solvent such as dry dimethyl formamide is treated with a base such as triethylamine under stirring for 30-90 minutes, preferably for 1 hour and the mixture is treated with isobutyl chloroformate. The mixture is further stirred for 30-90 minutes, preferably for 1 hour at room temperature and treated with L-glutamic acid diethyl ester hydrochloride. After about 1-3 hours, preferably 2 hours, the mixture is again treated one or more times with isobutyl chloroformate followed by L-glutamic acid diethyl ester hydrochloride and concentrated under high vacuum followed by digestion with ether and water to afford product N-[beta-(2,4-diaminopyrimido-[4,5-β]-pyrazin-6-yl)-6-ethylnicotinoyl ]-glutamic acid diethyl ester (I-6a).
Diester (I-6a) is dissolved in an alcohol solvent such as 2-methoxyethanol and a strong base such as 10% sodium hydroxide and water and stirred at room temperature for about 2-4 hours. The solution is then diluted with water, adjusted to pH 6 with an acid, such as acetic acid, and filtered to give the product N-[beta-(2,4-diaminopyrimido[4-5-beta-]-pyrazin-6-yl)-6-ethylnicotinoyl-] glutamic acid compound (I-7a). This compound is shown as compound 1 in the Table 1.
Other variations of pyridyl compounds are prepared in the same way including modifications which may be necessary depending on the target product.
Preparation of compounds according to the Reaction Scheme 2 is typically as follows.
2-Carbomethoxy-5-pyridylacetic acid methylester (II-1) is prepared from 5-methylpicolinic acid in a manner similar to preparation of compound I-1.
A solution of a strong base , such as potassium hydroxide in an aqueous alcohol, such as 90% methanol is treated with a solution of compound II-1 in an alcohol, preferably methanol. After about 2 hours, the pH of the solution is adjusted to pH 6.5 by addition of hydrochloric acid. The solution is concentrated in vacuo to give a solid that is a mixture of both monoesters, the dicarboxylic acid and the starting diester. The desired monoester (II-2) represents a major component of the mixture.
The mixture (II-2) in chloroform is cooled to about 0° C. and treated dropwise with a solution of diphenyldiazomethane dissolved in an organic solvent such as chloroform. The resulting mixture is stirred at ambient temperature for about 24 hours. The solution is washed with saturated sodium bicarbonate and water and the organic layer is dried, preferably over magnesium sulfate to give the product 2-carbomethoxy-5-pyridylacetic acid benzhydryl ester (II-3).
A cold suspension of sodium hydride in dry N,Ndimethylformamide was treated dropwise with a solution of II-3 in an organic solvent such as dry dimethylformamide. The mixture is stirred at about 0° C. for about 2 hours, cooled to about -25° C. and treated, dropwise with a solution of 2,4-diamino-6-bromomethylpteridine hydrobromide in dry dimethylformamide with maintenance of the temperature at -25° C. The mixture is stirred at about 20°-25° C. for about 2.5 hours, adjusted to about pH 8 by addition of dry ice concentrated in vacuo, washed with ether and water and dried to yield the product 3-(2,4-diaminopyrimido[4,5-betapyrazin-6-yl)-2-(2-carbomethoxypyrid-5-yl)propionic acid benzhydryl ester (II-4).
A mixture of the diester II-4 in dichloromethane is treated with an acid such as 99% trifluoroacetic acid. The solution is kept at room temperature for 15-90, preferably for 50 minutes, then concentrated at room temperature under vacuum. The residue is washed repeatedly with ether then dried in vacuo giving a solid. The solid is suspended in water and neutralized to about pH 6-7 with 1.5M ammonium hydroxide. The product is collected by filtration and dried to give monocarboxylic acid II-5.
A solution of the monocarboxylic acid, II-5 dissolved in dimethylsulfoxide is stirred at a temperature of about 130° for about 30 minutes. The solution is concentrated under high vacuum and the residue was washed with ether and water. The solid is collected and dried in vacuo at room temperature to afford beta-[3-(2,4-diaminopyrimido[4,5-B]-pyrazin-6-yl)]-4-ethylpicolinic acid methyl ester (II-6).
A mixture of the ester II-6 dissolved in an alcohol, such as 2-methoxyethanol is treated with water and then with a strong base such as 10% sodium hydroxide. After stirring for about 45 min, the solution is neutralized to a pH of about 7.5 with hydrochloric acid and concentrated under high vacuum to afford the product beta-[3-(2,4diaminopyrimido[4,5B]-pyrazin-6-yl)]-4-ethyl picolinic acid (II-7).
A mixture of the carboxylic acid (II-7) and an amine such as triethylamine, and dry dimethyl formamide is stirred at room temperature for about 15 min. Isobutyl chloroformate is added and the mixture is stirred for about 1 hour. L-Glutamic acid diethyl ester hydrochloride is added and the mixture is stirred for about 2 hours. The addition of isobutyl chloroformate and diethyl glutamate is repeated at about one-half the initial quantities and the final mixture is stirred for about 16 hours. After filtration, the filtrate is concentrated in vacuo to yield the diester beta-[3-(2,4)-diaminopyrimido (4,5-b)-pyrazin-6-yl)]-4-ethylpicolinoyl]glutamic acid diethyl ester (IIS).
The diester (II-8) is dissolved in an alcohol such as 2-methoxyethanol and 10% sodium hydroxide is added. The mixture is stirred for about 2 hours at room temperature. The pH of the solution is adjusted to about pH 5-6 with acetic acid and evaporated in vacuo. The residue is treated with water , adjusted to pH 3-4 and the product is collected to give beta-[3-(2,4)-diaminopyrimido[4,5-B]-pyrazin-6-yl]-4-ethylpicolinoyl]glutamic acid (II-9). This compound is shown in Table 1 as compound 3.
Preparation of thiophene analogues of 10deazaaminopterins is illustrated in Reaction Scheme 3.
Starting compounds III-1 and III-2, namely 5-methylthiophene-2-carboxylic acid and methyl 5-methylthiophene-2-carboxylate, are commercially available from Sigma, St Louis, Mo. 5-Bromomethyl-2-carbomethoxythiophene (III-3) is prepared from 5-methylthiophene-2-carboxylic acid by the method described in Tetrahedron, 23:2443-51 (1967).
A mixture of III-3, sodium cyanide, benzyltrimethylammonium chloride, dichloromethane, and water is stirred rapidly for about 16 hours. The mixture is then separated. The organic layer is treated with water, then with sodium cyanide, then with benzyltrimethylamonium chloride. This mixture is again rapidly stirred for about 24 hours. The organic layer is removed, dried over magnesium sulfate, and concentrated to give the product 5-cyanomethyl-2-carbomethoxythiophene (III-4).
A solution of III-4 and water in methanol is treated dropwise with a strong acid, such as sulfuric acid. This solution is stirred under argon at about 65° C. for 2-6, preferably for 4 days. The solution is poured onto ice water and extracted with ether twice. The organic extracts are combined and washed with water, saturated sodium bicarbonate then water again, dried over magnesium sulfate and concentrated to afford 2-carbomethoxythiophene-5-acetic acid methyl ester (III-5a).
A suspension of sodium hydride in dry dimethyl formamide is cooled to about 0° C. A solution of the diester (III-5a) in dry dimethyl formamide is added dropwise. The resulting mixture is stirred at about 0° C. for 15-90 minutes, preferably for about 1 hour, then cooled to about -30° C. and treated with a solution of 2,4-diamino-6-bromomethyl pteridine hydrobromide dissolved in dry dimethyl formamide. The resulting mixture is stirred for about 2.5 hours while rising to room temperature, then neutralized to about pH 8 by adding solid carbon dioxide. The mixture is concentrated under high vacuum, and the residue is washed and dried under high vacuum to give the product beta-(2,4-diaminopyrimido [4,5-B]pyrazin-6-yl)-alpha-carbomethoxy-5-ethyl-2-carbomethoxythiophene (III-6a).
A solution of the diester (III-6a) dissolved in an alcohol, such as 2-methoxy ethanol, water, and sodium hydroxide is stirred for about 1.5 hours. The mixture is filtered, and the filtrate is neutralized to about pH 7 with acetic acid and concentrated under high vacuum. The residue is suspended in water, and adjusted with acetic acid to about pH 5 to yield beta-(2,4-diaminopyrimido [4,5-B] pyrazin-6-yl)-alpha-carboxy-5-ethylthiophene-2-carboxylic Acid (III-7a).
A solution of the dicarboxylic acid (III-7a) in argon purged dimethylsulfoxide is placed in a 135° C. oil bath for about 45 min. The solution is then concentrated under high vacuum to a residue that is digested in ether which gives product beta-(2,4-diaminopyrimido[4,5-B]pyrazin-6-yl)-5-ethylthiophene-2-carboxylic acid (III-Sa).
A solution of the carboxylic acid (III-Sa) in dry dimethyl formamide is treated with triethyl amine and stirred at room temperature for about 1.25 hours. Isobutyl chloroformate is added, and the mixture is stirred for about 1 hour. L-Glutamic acid diethyl ester hydrochloride is added, and the mixture is stirred at room temperature for about 2 hours. Isobutyl chloroformate is then added, and the mixture is stirred for about 1 hour. The process is repeated several times. Concentration of the solution under high vacuum gave beta-(2,4-Diaminopyridimido[4,5-B]pyrazin-6-y)]-5-ethyl-2-thenoyl-glutamic acid diethyl ester (III-9a).
A mixture of the diester (III-9a) in an alcohol such as 2-methoxyethanol is treated with water and 10% sodium hydroxide. The mixture is stirred for about 1 hour, then adjusted to about pH 5.5 with 2-N hydrochloric acid and concentrated under high vacuum. The residue is digested in water and the mixture is filtered. The resulting solid is washed with water and dried to give beta-(2,4diaminopyrimidino[4,5-B]pyrazin-6-yl)-5-ethylthiophen-2-carboxyl-glutamic acid (III-10a). This compound is shown in Table 1 as compound 5.
II. 10-Alkenyl and 10-Alkynyl-10-Deazaaminopterins
In accordance with the present invention, 10-alkenyl and 10-alkynyl 10-deazaminopterin compounds II are provided having the formula: ##STR33## wherein R 1 and R 2 are selected from the group consisting of hydrogen, alkynyl and alkenyl having from one to about eight, preferably three to five carbon atoms with proviso that when one R 1 or R 2 is hydrogen then the other must be alkenyl or alkynyl.
Exemplary R 1 and R 2 alkenyl substituent includes allyl, crotyl (2-butenyl), 2-pentenyl, 4-pentenyl, 2-hexenyl, 5-hexenyl, 3-isopropenyl, 3-isobutenyl, and 2-octenyl.
Exemplary R 1 and R 2 alkynyl substituent includes propargyl, 2-butynyl, 3-butynyl, 2-pentynyl, 2-hexynyl, and 2-octynyl.
Process for preparing 10-alkenyl and 10-alkynyl 10-deazaminopterin compounds is illustrated in the Reaction Scheme 4. ##STR34##
Reaction Scheme 4 illustrates preparation of 10-alkenyl or 10-alkynyl deazaaminopterins
Step 1 is essentially an alkenylation or alkynylation of the homoterephthalic acid dimethyl ester by the corresponding alkyl, alkenyl or alkynyl bromide.
The reaction proceeds in the presence of an alkali metal hydride and is preferably carried out under anhydrous conditions at low temperatures, well below room temperature, and long reaction times in the presence of an inert polar solvent such as tetrahydrofuran. For example, the alkali metal hydride and solvent are mixed at 0° C., the homoterephthalic acid ester is added, and then the alkyl, alkenyl or alkynyl bromide, again at room temperature or below. The solvent can then be removed, and the reaction product worked up.
In Step 2 of the synthesis, the 2,4-diaminopteridine group is added to the 10-alkyl, alkenyl or alkynyl carbon atom of the homoterephthalic acid ester, again under anhydrous conditions in the presence of alkali metal hydride and a polar solvent, such as dimethyl formamide at low temperatures. The alkali metal hydride is mixed with the inert solvent at a low temperature, well below room temperature, and then a solution of an alpha-alkenyl of alpha-alkynyl homoterephthalic acid ester in the inert solvent is added.
Then the 2, 4-diamino-6-bromo methylpteridine is added slowly, while maintaining the low reaction temperature. After neutralization to about pH 7, the product is worked up.
The resulting 10-alkyl, 10-alkenyl or 10-alkynyl-10-carbomethoxy -4-deoxy-4-amino-10-deazapteroic acid methyl ester is then hydrolyzed to the corresponding 10-carboxy-10-deazapteroic acid in Step 3 with aqueous alkali such as sodium hydroxide, again at low temperature. The reaction mixture is then acidified and worked up.
The 10-carboxy-10-deazapteroic acid from Step 3 is readily decarboxylated in Step 4 by heating a solution in dimethyl sulfoxide at temperatures from 100° to about 160° C. Temperatures of 120°-140° C. were found to be optimal in most cases. Nearly quantitative yields of essentially pure, pale yellow product are routinely obtained. Solvents other than dimethyl sulfoxide may also be used in Step 4.
The resulting 4-amino-4-deoxy-10-deazapteroic acid is then converted to the 10-deazaminopterin compound in two steps. First, the product is reacted with diethyl-L-glutamate, converting the pteroic acid group to the corresponding glutamate, diethyl ester, and the esterifying ethyl groups are then hydrolyzed by reaction with dilute aqueous alkali, such as aqueous sodium hydroxide, forming the free glutamic diacid group of the 10-deazaminopterin compound.
The Step 5 reaction requires an acid acceptor to take up the liberated hydrogen chloride. The Step 5 reaction may be conducted with other alkyl chloroformates such as methyl, ethyl, etc. Acid acceptors are preferably organic bases such as tertiary amines or substituted pyridines, for example, triethylamine, tributylamine, N-methylmorpholine, collidine and lutidine. The diethyl glutamate may be added as the free base or as the hydrochloride salt in the presence of an additional equivalent of the acid acceptor.
The reaction proceeds at room temperature or below, and an inert solvent can be used. The isobutyl chloroformate can be added slowly to the reaction mixture, and upon completion of the reaction, diethyl-L-glutamate, organic amine and more solvent can be added, and reaction continued at the same temperature until complete.
The reaction mixture is worked up by removing the solvent by evaporation, preferably in vacuo, and stirring the residue with a mildly alkaline aqueous solution, such as aqueous sodium bicarbonate. The diester is insoluble, and can be recovered by filtration, while unreacted pteroic acid dissolves in the alkaline solution.
Hydrolysis of the esterifying ethyl groups in Step 6 is carried out with aqueous alkali at room temperature. The diester can be dissolved in a suitable solvent, such as 2-methoxyethanol, and held in the presence of the aqueous alkali until hydrolysis is complete. The acidic 10-deazaminopterin compound is soluble in aqueous alkali, and can then be precipitated by addition of acid, such as glacial acetic acid. The precipitate can be recovered, washed and dried. The diester is readily hydrolyzed to the target compound, such as for example 10-propargyl-10-deazaaminopterin compound IV-6b.
Using the above procedure, with decarboxylation of a 10-carboxypteroic acid intermediate, the following deazaaminopterin analogues have been prepared: 10-allyl-10-deazaaminopterin; 10-propargyl-10-deazaaminopterin; 10-propyl-10-deazaaminopterin; 10-allyl-8, 10dideazaaminopterin; 10-propyl-8, 10-dideazaaminopterin; 8, 10-dideazaminopterin; 5, 10-dideazaminopterin; 5-CH 3 -5, 10dideazaaminopterin; 5-CH 3 -10-C 2 H 5 -5, 10-dideazaaminopterin.
Compound IV-6b was tested in murine leukemia cells test and also for its inhibitory effect on the growth of the mammalian tumor.
Pharmaceutical Compositions
Compounds of the current invention are useful in the method of treatment of rheumatoid arthritis and as active neoplastic agents.
The 10-deazaaminopterin compound of the current invention can be administered per se, or in association with a pharmaceutically acceptable diluent or carrier. The invention accordingly also provides a pharmaceutical composition in dosage unit form comprising from 0.1 to about 500 mg of 10-deazaaminopterin compound, per dosage unit, together with a pharmaceutically acceptable nontoxic inert excipient, carrier or diluent.
The 10-deazaaminopterin compound can be formulated in the form of an acid addition salt. These salts are formed with one or more free NH2 groups of the heteroaroyl-10-deazaaminopterin molecule. Typically, the compounds are injected in the form of their sodium salts in aqueous solution. Other salts, such as K, Ca, NH 4 , and the like, could be used as prepared from the appropriate hydroxide or carbonates.
The acid addition salts are the pharmaceutically acceptable, nontoxic addition salts with suitable acids, such as those with inorganic acids, for example, hydrochloric, hydrobromic, nitric, sulphuric, and phosphoric acids, and with organic acids, such as organic carboxylic acids, for example, glycolic, maleic, hydroxymaleic, malic, tartaric, citric, salicylic, acetyloxybenzoic, nicotinic, and isonicotinic acid, and organic sulphonic acids, for example, methanesulphonic, ethanesulphonic, 2-hydroxyethanesulphonic, toluene-psulphonic, and naphthalene-2-sulphonic acid.
An acid addition salt can be converted into the free compound according to known methods, for example, by treating it with a base, such as with a metal hydroxide or alkoxide, for example, an alkali metal or alkaline earth metal hydroxide, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide; with a metal carbonate, such as an alkali metal or an alkaline earth metal carbonate or hydrogen carbonate, for example, sodium, potassium or calcium carbonate or hydrogen carbonate, with ammonia; or with a hydroxyl ion exchange resin, or with any other suitable reagent.
An acid addition salt may also be converted into another acid addition salt according to known methods, for example, a salt with an inorganic acid may be treated with a metal salt, for example a sodium, barium or silver salt, of an acid in a suitable diluent, in which a resulting inorganic salt is insoluble and is thus removed from the reaction medium. An acid-addition salt may also be converted into another acid addition salt by treatment with an anion exchange preparation.
The glutamic acid COOH groups can also be in salt form, as the ammonium NH 4 , alkali metal salts (Na + , K + ), or the nontoxic alkaline earth metal salts (Ca ++ ) of the glutamate COOH groups.
The 10-deazaaminopterin compound or salt thereof can be administered to the mammal, including human, by any available route, including oral and parenteral (intravenous, intraperitoneal, subcutaneous, and intramuscular) administration. The amount administered is sufficient to ameliorate the arthritis or other proliferative disease, and will depend upon the type of arthritis, the species of animal, and the weight of the animal. For example, in human administration, a dosage of 10-deazaaminopterin compound within the range from about 0.1 mg/kg to about 500 mg/kg per day should be sufficient. Dosages exceeding the higher part of the range are normally administered in conjunction with leucovorin, 5-formyl tetrahydrofolate, to reduce toxicity. The upper limit of dosage is that imposed by toxic side effects, and can be determined by trial and error for the animal to be treated, including humans.
To facilitate administration, the 10-deazaaminopterin compound or salt thereof can be provided in composition form, and preferably in dosage unit form. While the compound can be administered per se, it is normally administered in conjunction with a pharmaceutically acceptable carrier therefor, which dilutes the compound and facilitates handling. The term "pharmaceutically acceptable" means that the carrier (as well as the resulting composition) is sterile and nontoxic.
The carrier or diluent can be solid, semisolid, or liquid, and can serve as a vehicle, excipient, or medium for the heteroaroyl-10-deazaaminopterin compound. Exemplary diluents and carriers include lactose, dextrose, sucrose, sorbitol, mannitol, starches, gun acacia, calcium phosphate, mineral oil, cocoa butter, oil of theobroma, alginates, tragacanth, propylhydroxybenzoate, talc, or magnesium stearate.
For convenience in handling, the 10-deazaaminopterin compound and carrier or diluent can be enclosed or encapsulated in a capsule, sachet, cachet, gelatin, paper or other container, especially when intended for use in dosage units. The dosage units can for example take the form of tablets, capsules, suppositories, or cachets.
UTILITY
Compounds of the current invention are useful for treatment and prevention of arthritis, particularly rheumatoid arthritis, for suppression of neoplastic growth in tumors, such as mammary tumors, and for suppression of neoplastic growth of blood forming tissues, particularly for treatment of leukemia.
The biological activity of the compounds of the current invention was tested in vitro in culture cells and in vivo in mammals.
The antiarthritic efficacy evaluation used a mouse model of inflammatory disease that occurs in response to an antigenic challenge with Type II collagen according to method described in Nature, 283,666-668 (1980).
The fundamental aspects of the mouse model allow it to serve as a representative presentation of human disease. The parallels between the known aspects of the mouse model and rheumatoid arthritis include a humoral response in which antibodies are produced to an antigen that is present in the joint tissue and the antigenic challenge is accompanied by cell-mediated aspects of immunity. The resultant inflammation of the joint tissue yields facets of periostitis, synovial lining hyperplasia, degradation of bone and cartilage and pannus and new bone formation.
Antineoplastic activity of the compounds of the current invention was tested by the effect of 10-propargyl-10-deazaaminopterin on growth inhibition of L 1210 murine leukemia cells in culture and for its ability to inhibit dihydrofolate reductase derived from L 1210 cells.
The used method was according to Biochem. Pharmacol., 28:2993-2997 (1973). Enzyme was derived from L 1210 murine leukemia cells. The inhibition was conducted at pH 7.3. Data were analyzed according to method described in Biochem J., 135:101-107 (1973). Methotrexate was used as a control.
In vivo effect of 10-propargyl-10-deazaaminopterin in suppression of the tumor growth was evaluated in the EO771 murine mammary tumor model according to method described in Proc. Ann. Soc. Clin. Oncol., 11:51 (1992).
Tumor evaluation was performed in EO771 solid subcutaneous mammary tumor in BDF1 female mice. The mice were injected with tested compound with doses as indicated in Table 6. Results are described in Example 16. Methotrexate was not as effective in this assay. The EO771 solid tumor model is predictive for activity in human breast cancer as demonstrated by 10-ethyl-10-deazaminopterin (Edatrexate).
The following Examples are intended to illustrate the preparation of representative compounds, methods and procedures of this invention. They are not to be interpreted to limit the scope of this invention in any way.
EXAMPLE 1
N-[Beta-(2,4-Diaminopyrimido-[4,5-B-]-pyrazin-6-yl)-6 ethylnicotinoy] glutamic Acid (I-7a).
This example illustrates a preparation of N-[beta(2,4-diaminopyrimido-[4,5-B-]-pyrazin-6-yl)-6-ethylnicotinoyl-] glutamic Acid (I-7a) according to the procedure illustrated in the Reaction Scheme 1. The compound is listed in the Table 1 as compound 3.
5-Carbomethoxy-2-pyridylacetic Acid Methyl Ester (I,! ).
Freshly distilled diisopropylamine (7.4 g, 73 mmol) in dry tetrahydrofuran (100 mL) was cooled under argon to 0° C., then treated dropwise with n-butyl lithium in hexane (50 mL of a 1.6-M solution) and stirred at 0° C. for 1 hour. The lithium diisopropyl amide solution was added dropwise over 45 minutes to a -25° C. mixture of 6-methylnicotinic acid (4.0 g., 29 mmol) and hexamethylphosphorous triamide (5.23 g) in dry tetrahydrofuran. The solution became red. The temperature of the red solution was allowed to rise to 0° C. whereupon stirring was continued for 2 hours. Carbon dioxide was bubbled through the 0° C. solution, resulting in a yellow precipitate. The mixture was allowed to rise to room temperature and was stirred for 16 hours. Filtration gave a yellow solid that was suspended in methanol (50 mL) and the mixture was cooled to 0° C. Saturated methanolic HCl was added, and the solution was stirred at room temperature for 72 hours. Concentration in vacuo gave a residue that was partitioned between ether and saturated sodium bicarbonate. The ether layer was washed with water, dried over magnesium sulfate, and concentrated to an orange oil. Chromatography on flash silica gel (5% ethyl acetate in hexanes) gave the product I-la as a yellow solid yielding 1.84 g (30%). M.p. 56°-57°.
Analysis gave the following results. NMR (CDCl3): delta 9.10 (m, 1H, 6-H); 8.21 (m, 1H, 4-H); 7.33 (m, 1H, 3H) 3.84 (m, 8H, CH 2 COOCH 3 +ArCOOCH 3 ). Anal. Calcd. for C 10 H 11 NO 4 : C, 57.41%; H, 5.30%; N, 6.70%. Found: C, 57.53%; H, 5.33%; N, 6.54%.
Alpha-ethyl-5-carbomethoxy-2-pyridylacetic Acid Methyl Ester (I-2)
A 0° C. suspension of sodium hydride (1.14 g, 50% in oil, 0.57g of sodium hydride, 23.8 mmol) in dry dimethyl formamide was treated dropwise with a solution of I-I (4.98 g, 23.8 mmol) in dry dimethyl formamide (15 mL). This mixture was stirred at 0° C. for 1 hour, then cooled to 30° C. A solution of ethyl iodide (3.72 g, 23.8 mmol) in dry dimethyl formamide (50 mL) was added dropwise, maintaining a -25° C. reaction temperature, then stirred for 2 hours at room temperature. The reaction was neutralized to pH 8 by adding solid carbon dioxide, then concentrated under high vacuum. The residue was partitioned between ether and water. The organic layer was washed with 10% sodium bicarbonate, 10% sodium bisulfite, and water. The organic layer was dried over magnesium sulfate and concentrated to a pale brown oil. Chromatography on flash silica gel (5% ethyl acetate in hexane) gave the product I-2 as a yellow oil (2.86 g, 51%) that was pure by TLC (10% ethyl acetate in hexanes on silica gel). Analysis gave the following results.
NMR (CDCl 3 ) delta 9.13 (m, 1H, 6-H); 8.26 (m, 1H, 4-H); 7.39 (m, 1H, 3-H); 3.83 (m, 7H, 2 X OCH 3 +alpha-CH); 2.10 (m, 2H, CH 2 CH 3 ); 0.87 (t, 3H, CH 3 CH 2 ). Anal. Calcd. for C 12 H 15 NO 4 : C, 60.75%; H, 6.37; N, 5.90. Found: C, 60.63%; H, 6.38%; N, 5.89%.
3-(2,4-Diaminopyrimido[4,5-B]pyrazin-6-yl)-2-(3-carbomethoxypyrid-6-yl)-propionic Acid Methyl Ester (I-3a)
To a 0° C. suspension of sodium hydride (0.69 g of 50% sodium hydride in oil, 14.3 mmol) in dry dimethyl formamide (10 mL) was added dropwise a solution of I-2 (3.0 g, 14.3 mmol) in dry dimethyl formamide (10 mL). The mixture was stirred at 0° C. for 30 minutes, then cooled to -30° C. A solution of 2,4 diamino-6-bromomethylpteridine hydrobromide (4.8 mmol) in dry dimethyl formamide (30 mL) was added dropwise over 40 minutes. The reaction was stirred for 2.5 hours at 10° C., then adjusted to pH 8 by adding dry ice. Concentration under high vacuum gave a residue that was washed with ether, then water. Drying in vacuo at room temperature gave the product I-3a as a yellow solid, 1.8 g (99%).
Anal. Calcd. for C 17 H 17 N 7 O 4 . 17 H 2 O: C, 49 32%; H, 4.96%; N, 23.68%. Found: C, 49.56%; H, 4.21; N, 23.25%.
Beta-(2,4-Diamino-[4,5-B]pyrazin-6-yl)-6-ethylnicotinic Acid (I-5a)
A solution of the diester I-3a (1.8 g, 4.7 mmol) in 2-methoxyethanol (20 mL), water (20 mL), and 10% sodium hydroxide (20 mL) was stirred for 2.5 hours, then diluted with water (40 mL). The reaction was adjusted to pH 6 with glacial acetic acid. The cream-colored precipitate was collected, washed with water, and dried to yield 1.61 g (58%) of product I-4a. HPLC indicated 95.3% purity.
A mixture of the dicarboxylic acid I-4a (0.5 g, 1.4 mmol) in dry argon-purged dimethyl sulfoxide (40 mL) was heated to 110° C. for 25 minutes, then concentrated under high vacuum. The residue was suspended in water (40 mL), and sufficient ammonium hydroxide was added to produce a solution. The solution was adjusted to Ph 5 by dropwise addition of glacial acetic acid, then the precipitate was collected. The resulting yellow solid was washed with water and dried to yield 0.4 g (94%) of product I-5a.
HPLC shows 92% purity. Analysis gave the following results. Mass spectrum m/e 527 (TMS3). Anal. Calcd. for C 14 H 13 N 2 O 2 . 2.0 H 2 O: C, 48.41%; H, 4.93; N, 28.23. Found: C, 48.95; H, 4.89; N, 27.79.
N-[Beta-(2,4-Diaminopyrimido-[4,5-B]-pyrazin-6-yl)-6ethylnicotinoyl]-glutamic Acid Diethyl Ester (I-6a)
A mixture of the carboxylic acid I-5a (0.4 g, 1.25 mmol) in dry dimethyl formamide was treated with triethyl amine (1.2 g, 11.8 mmol). After being stirred for 1 hour, the mixture was treated with isobutyl chloroformate (0.35 g, 2.6 mmol). The mixture was stirred for 1 hour at room temperature and treated with L-glutamic acid diethyl ester hydrochloride (0.62 g, 2.6 mmol). After 2 hours, the mixture was treated with isobutyl chloroformate (0.18 g, 1.3 mmol). The mixture was stirred for 1 hour and treated with L-glutamic acid diethyl ester hydrochloride (0.31 g, 1.3 mmol). After 1 hour of stirring, isobutyl chloroformate (0.18 g, 1.3 mmol) was added. The mixture was stirred for additional 1 hour. L-glutamic acid diethyl ester hydrochloride (0.31 g, 1.3 mmol) was added, and the mixture was stirred for 16 hours. The mixture was concentrated under high vacuum. The residue was washed thoroughly with ether, then with water. The residue was crystallized from hot ethanol, giving yellow crystals (0.31 g, 50% theory) of product I-6a. Analysis gave the following results.
TLC (20% methanol in chloroform on silica gel plates) Rf=0.2; mass spectrum m/e 497 (M+H). Anal. Calcd. for C 23 H 28 N 8 O 5 . H 2 O: C, 53.68%; H, 5.87%; N, 21.77%. Found: C, 53.45%; H, 5.70%; N, 21.78%. NMR (d 6 DMSO) delta 8.90 (d, 1H, NHCO); 8.87 (d, 1H, pyr 6'-H), 8.61 (s, 1H, Cv-H); 8.10 (m 1H, pyr 4'-H); 7.70 (broad d. 1H, NH); 7.42 (d, 1H, pyr 3'-H); 6.65 (broad s, 2H, NH 2 ); 4.40 (m, 1H, CHN); 4.05 (m, 4H, 2 X OCH 2 ); 3.30 (CH 2 CH 2 +H 2 O); 2.45 (t, 2H, CH 2 CO 2 ); 2.05 (m, 2H, CH 2 CH); 1.70 (t, 6H, 2 X CH 3 ).
N-[Beta-(2,4-diaminopyrimido-[4-5-β-]-pyrazin-6-yl)-6-ethylnicotinoyl-] glutamic Acid CI-7a) (Compound No. 1)
Diester I-6a (0.3 g, 0.6 mmol) was dissolved in 2-methoxyethanol (10 mL), 10% sodium hydroxide (5 mL) and water (4 mL) and stirred at room temperature for 2.5 hours. The solution was then diluted with water (20 mL), adjusted to pH 6 with acetic acid, and filtered. The resulting yellow solid was washed with water and dried to give the product I-7a as a fine powder (0.19 g, 71%). HPLC (see above conditions) shows 95% purity. Analysis gave the following results.
Mass spectrum m/e 729 (TMS 4 M+H); UV (0.1N NaOH) 258 nm (25,000) 275 sh (13, 900), 371 (6,600). Anal. Calcd. for C 19 H 20 N 8 O 5 , 2,25 H20: C, 47.44%; H, 5.14%, N, 23.30%. Found: C, 47 04%; H, 4 64%; N 23.64%.
EXAMPLE 2
N-[Alpha-Ethyl-beta-(2,4-diaminopyrimido-[4,5-β]-pyrazin-6-yl)-6-ethylnicotinoyl]-glutamic Acid (I-7b)
This example illustrates a preparation of N-[alpha-ethyl-beta-(2,4-diaminopyrimido-[4,5-β]-pyrazin-6-yl)-6-ethylnicotinoyl]-glutamic acid (I-7b) according to procedure illustrated in the Reaction Scheme 1. Example yields compound 2, listed in Table 1.
3-(2,4-Diaminopyrimido[4,5-β]-pyrazin-6-yl)-2-(3-carbomethoxypyrid-6-yl) -2-ethylpropionic Acid Methyl Ester (I-3b)
A 0° C. suspension of sodium hydride (0.56 g, 50% in oil, 11.8 mmol of sodium hydride) in dry dimethyl formamid, (10 mL) was treated dropwise with a solution of the diester I-2 (2.8 g, 11.8 mmol) in dry dimethylformamide (10 mL). The resulting mixture was stirred at 0° C. for 1 hour, then cooled to -30° C. A solution of 2,4-diamino-6-bromomethylpteridine hydrobromide (3.9 mmol) in dry dimethyl formamide was added, maintaining a -25° C. internal temperature. The reaction mixture was allowed to stir for 2 hours as it rose to room temperature. The mixture was adjusted to pH 8 by adding solid carbondioxide. Concentration under high vacuum gave a residue that was washed with ether, then water. The resulting yellow solid was dried in vacuo, giving 1.26 g (78%) of product I-3b. Analysis gave the following results.
Mass spectrum m/e 412 (M+H). NMR (d 6 DMSO) delta 9.04 (s, 1H, C7-H); 8.23 (m, 2H, pyr 5'-H+pyr 4'-H); 7.45 (d, 1H, pyr 2'-H) ;6.62 (broad s, 2H, NH2); 3.87 (s, 3H, ArCOOCH 3 ); 3.62 (m, 5H, C 10 COOCH 3 +C 9 -H 2 ); 2.01 (m, 2H, CH 2 CH 3 ); 0.80 (t, 3H, CH 3 CH 2 ). Anal Calcd. for C 19 H 21 N 7 O 4 . 1.5 H 2 O: C, 52.04%; H, 5.51%; N, 22.36%. Found: C, 52.22%; H, 5.18%; N, 22.49%.
3-(2,4-diaminopyrimido[4,5,β]pyrazin-6-yl),2(3-carboxypyrid-6-yl)-2-ethylpropionic Acid (I-4b)
A solution of the diester I-3b (1.24 g, 3.0 mmol) in 2-methoxyethanol (20 mL), water (20 mL), and 10% sodium hydroxide (20 mL) was stirred for 15 hours. The reaction was adjusted to pH 7 with glacial acetic acid, then concentrated under high vacuum. The residue was treated with water (10 mL) and adjusted to pH 4 with 4N hydrochloric acid, and the precipitate was collected. The resulting tan solid washed with water and dried in vacuo yielded 0.31 g (27%) of product I-4b.
Alpha-ethyl-beta-(2,4-diaminopyrimido-[4,5-b]-pyrazin-6 yl)-6-ethyl nicotinic Acid (I-5b)
The dicarboxylic acid I-4b (0.31 g) was dissolved in dry dimethyl formamide (8 mL). The solution was allowed to stand at room temperature for 20 minutes. Concentration under high vacuum gave a residue that was washed with ether. The resulting tan solid was dried in vacuo to give the product I-5b in 99% yield. HPLC showed the product to be of 90% purity.
N-[Alpha-ethyl-beta-(2,4-diaminopyrimido-[4,5-beta]-pyrazin-6-yl)-6-ethyl-nicotinoyl]-glutamic Acid Diethyl ESter (I-6b)
A mixture of the carboxylic acid I-5b (0.31 g, 0.75 mmol) and triethylamine (0.73 g, 7.2 mmol) in dry dimethyl formamide (20 mL) was stirred at room temperature for 15 minutes. Isobutyl chloroformate (0.22 g, 1.6 mmol ) was then added, and the mixture was stirred for 1 hour. L-Glutamic acid diethyl ester hydrochloride (0.38 g, 1.6 mmol) was added, and the mixture was stirred for 2 hours. Isobutyl chloroformate (0.11 g, 0.8 mmol) was added, and the mixture was stirred for 1 hour. L-Glutamic acid diethyl ester hydrochloride (0.19 g, 0.8 mmol) was added, and the mixture was stirred at room temperature for 1 hour. Isobutyl chloroformate (0.11 g, 0.8 mmol) was added, and the mixture was stirred for 1 hour. L-Glutamic acid diethyl ester hydrochloride (0.19 g., 0.8 mmol) was added, and the mixture was stirred for additional 16 hours. The mixture was filtered and the filtrate concentrated under high vacuum. The residue was chromatographed on flash silica gel (5% methanol in chloroform eluent), giving the product I-6b as an orange glass (0.23 g, 48%). Analysis gave the following results.
Mass spectrum m/e 525 (M+H) ; NMR (CDCl 3 ) delta 9.01 (broad s, 1H, pyr 6'-H; 8.45 (broad s, 1H, 7-H); 7.97 (d, 1H, pyr 4'-H); 7.35 (broad s, 2H, NH 2 ); 7.08 (d, 1H, pyr 3'-H); 5.38 (broad s, 2H, NH 2 ); 4.75 (m, 1H, CHN): 4.19 (m, 4H, 2 X OCH 2 ); 3.32 (m, 3H, C 9 -H 2 +C 10 -H); 2.50 (m, 2H, C 10 -CH 26l ); 2.23 (m, 4H, glu C 4 -H 2 +glu C 3 -H 2 ); 1.26 (m, (6H, 2 X OCH 2 CH 3 ); 0.83 (t, 3H, C 10 -CH 2 CH 3 )/
N-[Alpha-ethyl-beta-(2,4,-diaminopyrimido-[4,5-beta]-pyrazin-6-yl)-6-ethylnicotinoyl]-glutamic Acid (I-7 b, Compound No. 2 )
The diester I-6b (0.2g, 0.38 mmol ) was dissolved in 2-methoxyethanol (6 mL) and 10% sodium hydroxide (1.6 mL) and stirred for 1 hour at room temperature. The solution was adjusted to pH 7 with acetic acid and concentrated under high vacuum. The residue was dissolved in water (7 mL) and acidified to pH 3 with 4M hydrochloric acid, then filtered. The resulting tan solid was washed with water and dried in vacuo to yield 70 mg (39%) of product I-7b. HPLC (see above conditions) showed 98.9% purity. Analysis gave the following results.
Mass spectrum m/e 757 (TMS 4 ), (M+H) ; UV (0.1N NaOH) 256 nm (25,246) 367 (6562). Anal. Calcd. for C 21 H 24 N 8 O 5 . 1.4 H 2 O: C, 51.09%; H, 5.47%; N, 22.68%. Found: C, 51.12%; H, 5.29%; N, 22.55%.
EXAMPLE 3
Beta-[3-(2,4)-Diaminopyrimido[4,5-β]-pyrazin-6-yl]-4-ethylpicolinoyl]glutamic Acid
This example illustrates a preparation of beta-[3(2,4)-diaminopyrimido[4,5-β]-pyrazin-6-yl]-4ethylpicolinoyl]glutamic acid (III-9) according to procedure illustrated in the Reaction Scheme 2. The resulting compound is listed in Table 1 as compound 5.
2-Carbomethoxy-5-pyridylacetic Acid Methyl Ester (II-1)
The diester (II-1) was prepared in a manner similar to that of preparation of compound I-1 from 5-methylpicolinic acid (10.0 g, 73 mmoles) resulting in an amber oil product in 49% yield. Analysis gave the following results.
NMR (CDCl 3 ): delta 8.63 (d, 1H, C 3 -H); 8.15 (d, 1H, C 6 -H); 7.81 (m, 1H, C 4 -H); 4.02 (s, 3H ArCOOCH 3 ); 3.75 (s, 5H, CH 2 COOCH 3 ).
2-Carbomethoxy-5-pyridylacetic Acid Benzhydryl Ester (11-3)
A solution of potassium hydroxide (1.39 g, 24.8 mmoles) in 90% methanol (100 mL) was treated with a solution of compound II-1 (5.18 g, 24. 8 mmoles) in methanol (14 mL). After 2 hours the solution was adjusted to pH 6.5 by hydrochloric acid addition. The solution was concentrated in vacuo to give a tan solid that was a mixture of both monoesters, the dicarboxylic acid and the starting diester. HPLC indicated the desired monoester (II-2) to represent 57% of the mixture.
The mixture of compound II-2 in chloroform (100 mL) was cooled to 0° C. and treated dropwise with a solution of diphenyldiazomethane (5.27 g, 27.2 mmoles) in chloroform (50 mL). The resulting purple mixture was stirred at ambient temperature for 24 hours. The solution was washed with saturated sodium bicarbonate and water. The organic layer was dried over magnesium sulfate and concentrated to a purple syrup. Crystallization from pentane gave the product II-3 as a white solid, 1.86 g (21% yield from II-1). Analysis gave the following results.
NMR (CDCl 13 ): delta 8.68 (m, 1H, C3-H); 8.10 (d, 1H C6-H); 7.75 (m, 1H, C 4 -H); 7.30 (m, 10H, 2 x C 6 H 5 ); 6.90 (s, 1H, OCH); 4.05 (s, 3H, OCH 3 ); 3.81 (s, 2H, CH 2 ). Anal. Calcd. for C 22 H 19 NO 4 . 0.25 H 2 O: C, 72.21; H, 5.37; N, 3.83. Found C, 72.43; H, 5.49; N, 3.69. TLC (40% ethyl acetate in hexanes on silica gel) showed a single spot at Rf 0.5.
3-(2,4-Diaminopyrimido[4,5-β-pyrazin-6-yl)-2-(2-carbomethoxypyrid-5-yl)propionic Acid Benzhydryl Ester (II-4)
A 0° C. suspension of sodium hydride (413 mg of 50% in oil, 8.6 mmoles) in dry N,N-dimethylformamide (20 mL) was treated dropwise with a solution of compound II-3 (3.11 g, 8.6 mmoles) in dry dimethylformamide (25 mL). The yellow-green mixture was stirred at 0° C. for 2 hours, becoming a red solution. This was cooled to -25° C. and treated, dropwise with a solution of 2,4-diamino-6-bromomethylpteridine hydrobromide (3.4 mmoles) in dry dimethylformamide (20 mL) with maintenance of the temperature at -25° C. The mixture was stirred at 22° C. for 2.5 hours and adjusted to pH 8 by addition of dry ice. Concentration under high vacuum gave a residue which was washed with ether and water. The yellow solid was dried in vacuo and chromatographed on flash silica gel using 4% methanol in chloroform as eluant to yield the product II-4 as a yellow powder 1.33 g (75% yield). Analysis gave the following results.
NMR (CDCl 3 ): delta 8.80 (m, 1H, CT-H); 8.62 (s, 1H, C 3 '-H); 8.10 (d, 1H, C 6 '-H); 7.84 (m, 1H, C 4 '-H); 7.20 (m, 12H, 2 x C 6 H 5 +NH 2 ); 6.80 (s, 1H, OCH); 5.20 (broad s, 2H, NH 2 ); 4.55 (m, 1H, C 10 -H); 4.02 (s, 3H, OCH 3 ); 3.85 (m, 1H, C 9 -H); 3.30 (m, 1H, Cg-H).
beta- (2,4 -Diaminopyrimido[4,5-β]-pyrazin-6-yl)-4-ethylpicolinic Acid Methyl Ester (II-6)
A mixture of the diester II-4 (1.29 g, 2.4 mmoles) in dichloromethane (67 mL) was treated with 99% trifluoroacetic acid (33 mL). The yellow solution was kept at room temperature for 50 minutes then concentrated at room temperature under high vacuum. The residue was washed repeatedly with ether then dried in vacuo giving a bright yellow solid. This was suspended in water and neutralized to pH 6 with 1.5 M ammonium hydroxide. The mixture was concentrated under high vacuum giving a yellow solid product II-5, 0.99 g. HPLC confirmed the conversion to II-5.
A solution of the monocarboxylic acid, II-5 (0.99 g crude) in 40 mL of dimethylsulfoxide, was stirred at 130° for 30 minutes. HPLC showed disappearance of the starting carboxylic acid (II-5) at retention time 4.4 minutes and the desired monoester to be present (retention time 15.2 minutes). The solution was concentrated under high vacuum and the residue was washed with ether and water. The orange solid was collected and dried in vacuo at room temperature to afford 505 mg (64%) of product II-6.
NMR (CDCl 3 ): delta 8.60 (m, 2H, C 7 -H, 6'-H); 8.10 (d, 1H, 3'-H); 7.85 (d, 1H, 5'-H); 7.20 (m, 3H, NH 2 ); 4.00 (s, 3H, OCH3); 3.35 (s, 4H, CH 2 CH 2 ).
Beta-(2,4-diaminopyrimido[4,5-β]-pyrazin-6-yl)-4-ethyl picolinic Acid (II-7)
A mixture of the ester II-6 (0.49 g, 1.5 mmoles) in 2-methoxyethanol (5 mL) was treated with water (5 mL) then 10% sodium hydride (2.5 mL). After stirring 45 minutes, the resulting red solution showed complete saponification by HPLC.
The solution was neutralized to pH 7.5 with hydrochloric acid and concentrated under high vacuum. The resulting residue was treated with water and stirred.
Filtration gave 0.27 g of product as an orange solid (57%). HPLC showed 96% purity. Mass spectrum m/e 527 (TMS 3 ).
beta-[(2,4)-Diaminopyrimido (4,5-β)-pyrazin-6-yl)-4-ethylpicolinoyl]glutamic Acid Diethyl Ester (II-8)
A mixture of the carboxylic acid II-7 (0.27 g, 0.87 mmol) and triethylamine (822 mg, 8.12 mmol) in dry dimethyl formamide (15 mL) was stirred at room temperature for 15 minutes. Isobutyl chloroformate (0.23 mL, 1.78 mmole) was added and the mixture was stirred for 1 hour. L-Glutamic acid diethyl ester hydrochloride (427 mg, 1.78 mmol) was added and the mixture was stirred for 2 hours. The addition of isobutyl chloroformate and diethyl glutamate was repeated at one-half the initial quantities and the final mixture was stirred for 16 hours. After filtration, the filtrate was concentrated in vacuo and the residue was partitioned between water and chloroform. Chromatography of the chloroform soluble portion yielded 72 mg (18%) of the diester II-8. Analysis gave the following results.
NMR (CDCl 3 ): delta 8.60 (d, 1H, C 7 -H); 8.55 (d, 1H, NH); 8.43 (d, 1H, C 5 '-H);8.06 (d, 1H, C 2 '-H); 7.70 (m, 1H, C 6 '-H); 4.80 (m, 1H, CHNH); 4.20 (m, 4H, 2x OCH 2 ); 2.30 (m, 4H, glu CH 2 CH 2 ); 1.30 (m, 6H, 2x OCHC 2 CH 3 ). Mass spectrum m/e 496.
Beta-(2,4)-Diaminopyrimido[4,5-β]-pyrazin-6-yl-4-ethylpicolinoyl]glutamic Acid (II-9, Compound No. 5)
The diester II-8 (67 rag, 0.13 mmol) was dissolved in 2-methoxyethanol (2.3 mL) and 10% sodium hydroxide (2.2 mL) was added. The mixture was stirred for 2 hours at room temperature. The solution was adjusted to pH 5-6 with acetic acid and evaporated in vacuo. The residue was dissolved in 2 mL of water and acidified to pH 3-4. The solid was collected, washed with water, and dried to leave 34 mg (58% ) of product II-9.
HPLC shows 99.3% purity. UV (0.1 M NaOH) 257 (22,200); 371 (5,600). Mass spectrum m/e 729 (TMS 4 ).
EXAMPLE 4
Beta-(2,4-Diaminopyrimidino[4,5-β]pyrazin-6-yl)-5-ethyl-2-thenoyl-glutamic Acid
This example illustrates preparation of compound beta(2,4-Diaminopyrimidino[4,5-β]pyrazin-6-yl)-5-ethyl-2-theonyl-glutamic acid, as seen in Table 1, by the procedure illustrated in Reaction Scheme 3.
5-Methyl-2-Thenoic Acid and Its Methyl Ester (III-1 and III-2)
2-Methyl-2-thenoic acid (III-1) and its methyl ester (III-2) are commercially available and the source can be found, for example in Chemical Sources U.S.A. published annually by Directories Publishing, Inc. of Boca Ratan, Fla. or they can be readily prepared by methods known in the art.
5-Bromomethyl-2-carbomethoxythiophene (III-3).
This compound was prepared from 5-methylthiophene-2-carboxylic acid by the method of Gogte et al, Tetrahedron, 23, 2443-51 (1967).
5-Cyanomethyl-2-carbomethoxythiophene (III-4)
A mixture of III-3 (18.0 g, 76.6 mmol), sodium cyanide (15.0 g, 0.31 mmol), benzyltrimethylammonium chloride (1.75 g, 9.4 mmol), dichloromethane (75 mL), and water (75 mL) was stirred rapidly for 16 hours. The mixture was then separated. The organic layer was treated first with water (75 mL), then with sodium cyanide (15.0 g, 0.31 mmol), and last with benzyltrimethylamonium chloride (1.5 g, 8.0 mmol). This mixture was again rapidly stirred for 24 hours. The organic layer was removed, dried over magnesium sulfate, and concentrated. The residue was chromatographed on 250 g of flash silica gel using 20% ethyl acetate in hexane as an eluent, to give the product (III-4) as a yellow crystalline solid, 4.53 g (33%). Analysis gave the following results.
NMR (CDCl 3 ) d 7.66 (d, 1H, C 3 -H); 7.03 (d, 1H, C 4 -H); 3.83 (d, 5H, CH 3 +CH 2 ); mass spectrum m/e 196 (M +H); TLC (10% ethyl acetate in hexanes on silica gel plates); R f -0.3.
2-Carbomethoxythiophene-5-acetic Acid Methyl Ester (III-5a)
A solution of compound III-4 (0.5 g, 2.7 mmol) and water (0.2 g) in methanol (7.5 mL) was treated dropwise with concentrated sulfuric acid (1.5 mL). This solution was stirred under argon at 65° C. for four days. The pale yellow solution was poured onto ice-water (50 mL) and extracted with ether (2×50 mL). The organic extracts were combined and washed with water, followed with saturated sodium bicarbonate, then with water again, and dried over magnesium sulfate. The solution was concentrated to a clear, colorless oil that solidified to a white, waxy solid (0.4 g, 68%). Analysis gave the following results.
NMR (CDCl 3 ): delta 7.61 (delta, 1H, 3-H); 6.90 (delta, 1H, 4-H); 3.87 (m, 5H, ArCOOCH 3 +CH 2 ); 3.82 (s, 3H, CH 2 COOCH 3 ). TLC (10% ethyl acetate in hexane on silica gel) R f =0.4. Calc. C.sup. 9 H 10 O 4 S; C,50.46; H,4.70. Found: C,50,57; H, 4.79.
β]-(2,4-Diaminopyrimido[4,5-β]pyrazin-6-yl)-alphacarbomethoxy-5-ethyl-2-carbomethoxythiophene (III-6a)
A suspension of sodium hydride (0.84 g, 17.5 mmol) in 15 mL of dry dimethyl formamide was cooled to 0° C. A solution of the diester compound III-5a (3.73 g., 17.4 mmol) in 15 mL of dry dimethyl formamide was added dropwise. The resulting mixture was stirred at 0° C. for one hour, then cooled to -30° C. and treated with a solution of 2,4 diamino-6-bromomethylpteridine hydrobromide (16.1 mmol) in 40 mL of dry dimethyl formamide. The resulting mixture was stirred for 2.5 h while rising to room temperature, then neutralized to pH 8 by adding solid carbon dioxide. The mixture was concentrated under high vacuum, and the residue was washed with ether, then water, and dried under high vacuum to give the product III-6a as a yellow solid (1.98 g., 88% ). Analysis gave the following results.
Mass spectrum m/e 389 (M +H) . NMR (d 6 DMSO) delta 8.58 (s, 1H 7 -H); 7.60 (m, 3H, C 4 -H+NH 2 ); 7.12 (d, 1H, C 3 '-H); 6.61 (broad s, 2H, NH 2 ); 4.9 (t, 1H, C 3 '-H); 3.75 (s, 3H, C 2 '-COOCH 3 ); 3.63 (m, 5H, C 10 -COOCH 3 +C 9 -H 2 ).
Beta-(2,4-Diaminopyrimido[4,5,β]pyrazin-6-yl) -alpha-carboxy-5-ethylthiophene-2-carboxylic Acid (III-7a)
A solution of the diester III-6a (1.96 g, 5.05 mmol) in 30 mL of 2-methoxyethanol, water, and 30 mL of 2.5 M sodium hydroxide was stirred for 1.5 hours. The mixture was filtered, and the filtrate was neutralized to pH 7 with acetic acid and concentrated under high vacuum. The residue was suspended in water (30 mL) and adjusted with acetic acid to pH 5 to yield a precipitate. Filtration gave a tan solid that was digested in 95% ethanol. Filtration gave a tan solid that was washed with ether and dried in vacuo, yielding 1.31 g (77%) of product III-7a. Analysis gave the following results.
HPLC (Novapak C18 column, 25% methanol in 0.1 molar NaH 2 PO 4 , pH 6.5) indicated 92.2% purity; NMR (d 6 DMSO) delta 8.51 (s, 1H, C 7 -H); 7.55 (broad s, 2H, NH 2 ); 7.17 (d, 1H, 4'-H); 6.81 (d, 1H, 3'-H); 6.55 (broad s, 2H, NH2); 4.40 (t, 1H, C 10 -H); 3.15 (m, 2H, C 9 -H 2 ).
Beta-(2,4-Diaminopyrimido[4,5-β]pyrazin-6-yl )-5-ethylthiophen-2-carboxylic Acid (III-Sa)
A solution of the dicarboxylic acid III-7a (1.31 g, 3.64 mmol) in argon purged dimethylsulfoxide was placed in a 135° C. oil bath for 45 minutes. The solution was then concentrated under high vacuum to a residue that was digested in ether. Filtration yielded a brown solid that was washed with ether and dried in vacuo at room temperature to give 1.31 g of crude product, which was suspended in water (75 mL) and treated dropwise to pH 12 with ammonium hydroxide. The mixture was filtered and the filtrate adjusted to pH 5 with acetic acid. Filtration gave a brown solid that was dried in vacuo, yielding 0.97 g (84%) product III-Sa. Analysis gave the following results.
HPLC indicated 86% purity. Anal. Calcd. for C 13 H 12 N 6 O 2 S . H 2 O: C, 46.69%; H, 4.22%; N, 25.13%. Found: C, 46.80%; H, 4.01%; N, 24.82%.
Beta-(2,4-Diaminopyridimido[4,5-b]pyrazin-6-y1)-5-ethyl-2 Thenoyl-glutamic Acid Diethyl Ester (III-9a)
A solution of the carboxylic acid III-Sa (0.7 g, 2.2 mmol) in dry dimethyl formamide (40 mL) was treated with triethylamine (2.1 g, 21.0 mmol) and stirred at room temperature for 1.25 hours. Isobutyl chloroformate (0.63 g, 4.6 mmol) was added, and the mixture was stirred for 1 hour. L-Glutamic acid diethyl ester hydrochloride (1.1 g, 4.6 mmol) was added, and the mixture was stirred at room temperature for two hours. Isobutyl chloroformate (0.32 g, 2.3 mmol) was then added, and the mixture was stirred for one hour. L-glutamic acid diethyl ester hydrochloride (0.55 g, 2.3 mmol) was added, and the mixture was stirred for one hour. Isobutyl chloroformate (3.2 g, 2.3 mmol) was added, and the mixture was stirred at room temperature for one hour. L-Glutamic acid diethyl ester hydrochloride (0.55 g, 2.3 mmol) was added, and the mixture was stirred at room temperature overnight. Concentration under high vacuum gave a dark residue that was washed repeatedly with ether. The residue was then washed with dilute ammonium hydroxide, then water. The resultant orange solid was dried in vacuo. Chromatography on flash silica gel (2.5% methanol in chloroform) gave the product III-9a as a yellow powder, 0.32 g (32%). Analysis gave the following results.
NMR (d 6 DMSO+CDCl 3 ) d 8.5 (s, 1H, C 7 -H); 8.31 (d, 1H, NHC); 7.6 (d, 1H, 4'-H); 6.80 (d, 1H, 3'-H); 6.32 (broad s, 2H, NH 2 ); 4.54 (m, 1H, CHNH); 4.18 (m, 4H, 2 x OCH 2 ); 3.28 (m, C 9 -H 2 ); 2.42 (t, 2H, glu C 4 -H 2 ); 2.13 (m, 2H, glu C 3 -H 2 ); 1.28 (m, 6H, 2 x CH 3 CH 2 ).
Beta-(2,4-Diaminopyrimidino[4,5-β]pyrazin-6-yl)-5-ethyl-2-thenoyl-glutamic Acid (III-10a, Compound No. 5)
A mixture of the diester III-9a (0.26 g., 0.5 mmol) in 2-methoxyethanol (5 mL) was treated with water (5 mL) and 10% sodium hydroxide (5 mL). The mixture was stirred for one hour then adjusted to pH 5.5 with 2-N hydrochloric acid and concentrated under high vacuum. The residue was digested in water (5 mL) and the mixture was filtered. The resulting solid was washed with water and dried in vacuo at room temperature, giving 0.19 g (82%) of product III-10a. Analysis gave the following results.
HPLC shows 96.4% purity. UV (0,1N NaOH) 258 nm (28,310); 372 nm (6,737). NMR (d 6 DMSO) delta 8.67 (s, 1H, CT-H); 8.50 (d, 1H, NHCH); 8.00 (broad s, 2H, NH 2 ); 7.65 (d, 1H, 4'-H); 6.90 (broad s, 3H, 3'-H+NH 2 ); 4.30 (m, 1H, CHNH); 3.42 (m, C 9 -H 2 +C 10 -H 2 ); 2.35 (t, 2H, glu-C 4 -H 2 ); 1.95 (m, 2H, glu C 3 -H 2 ). Mass spectrum m/e 734 (TMS 4 ) (M+H). Anal. Calcd. for C 18 H 19 N 7 O 5 S . 2H 2 O: C, 44.90%; H, 4.81%; N, 20.36%. Found: C, 44.68%; H, 4.39%; N, 20.32%.
EXAMPLE 5
N-[Alpha-ethyl-beta-(2,4-diamino-[4,5,-β) -pyrazin-6 -yl)-5-ethyl-2-thenoyl]-Glutamic Acid
This example illustrates a preparation of N-[alpha-ethyl-beta-(2,4-diamino-[4,5-b)-pyrazin-6-yl)-5-ethylthiophene-2-carbonyl]-glutamic Acid (III-10b) according to the procedure illustrated in the Reaction Scheme 3. The compound is listed in Table 1 as compound 6.
Alpha-Ethyl-2-carbomethoxythiophene-5-acetic Acid Methyl Ester (III-5b)
A suspension of sodium hydride (0.59 g, 12.2 mmol ) in 20 mL of dry dimethyl formamide was cooled to 0° C. A solution of III-5a (2.60 g, 12.2 mmol) in 20 mL of dry dimethyl formamide was added, and the reaction was stirred for an additional hour at 0° C. The reaction was cooled to -30° C. and treated dropwise with a solution of ethyl iodide (1.9 g, 12.2 mmol) in dry dimethyl formamide, then stirred for 2.5 hours at 20° C. The solution was neutralized to pH 8 by adding solid carbon dioxide, then concentrated under high vacuum. The residue was digested in ether (250 mL) and filtered. The filtrate was washed with water, followed with saturated sodium bicarbonate, then with 10% sodium bisulfite and then with water again. The organic layer was dried on magnesium sulfate and concentrated. The residue was chromatographed on flash silica gel using ethyl acetate/hexane as an eluent, to yield 1.7 g (58%) product III-5b as a clear, colorless oil. Analysis gave the following results.
TLC (10% ethyl acetate in hexanes on silica gel plate), Rf=0.35. NMR (CDCl 3 ) delta 7.59 (d, 1H, Ar 3-H); 7.20 (d, 1H, Ar 4-H); 3.81 (m, 7H, 2 x OCH 3 +ARCH); 2.06 (m, 2H, CH 2 CH 3 ); 0.95 (t, 3H, CH 3 CH 2 ).
Beta-(2,4-Diaminopyrimido[4,5-β]pyrazin-6-yl)]-alphacarbomethoxy-alpha-ethyl-5-ethyl-2-carbomethoxythiophene (III-6b)
A mixture of sodium hydride (0.4 g, 8.3 mmol) in dry dimethyl formamide (25 mL) was cooled to 0° C. and treated dropwise with a solution of the diester III-5b (2.0 g, 8.3 mmol) in dry dimethyl formamide (25 mL), stirred at 0° C. for one hour, then cooled to -30° C. A solution of 2,4-diamino-6-bromomethylpteridine hydrobromide (2,7 mmol) in dimethylformamide (50 mL) was added dropwise, maintaining a -25° C. internal temperature, then stirred an additional 2.5 hours while warming to room temperature. The reaction was then adjusted to pH 8 with carbon dioxide and concentrated under a high vacuum to yield a yellow residue that was stirred in ether. Filtration gave a yellow solid which was washed with water and dried in vacuo to yield 0.97 g (85%) of product III-6b. Analysis gave the following results.
NMR (d 6 DMSO) delta 8.35 (s, 1H, CT-H); 7.78 (broad s, 1H, NH); 7.65 (d, 1H, C 4 '-H);7.17 (d, 1H, C 3 '-H); 6.65 (broad s, 2H, NH 2 ); 6.52 (broad s, 1H, NH); 3.77 (s, ArCOOOCH 3 ); 3.68 (s, CCOOCH 3 ); 2.06 (m, 2H, CH 2 CH 3 ); 0.76 (t, 3H, CH 3 CH 2 ). Mass spectrum m/e 416 (M+H).
Beta-(2,4-Diaminopyrimidino[4,5-β]pyrazin-6-yl) alpha-carboxy-alpha-ethyl-5-ethylthiophene-2-carboxylic Acid (III-7b)
A mixture of the diester III-6b (0.95 g, 2.3 mmol) in 2-methoxyethanol (15 mL), water (15 mL), and 15 mL of 10% sodium hydroxide (15 mL) was stirred for 3.5 hours. The solution was adjusted to pH 5 by dropwise addition of 2N HCl, and the resulting mixture was concentrated under high vacuum. The residue was digested in water, then filtered to yield a cream-colored solid that was washed with water, then dried in vacuo at room temperature, giving 0.51 g (58%) of product III-7b. HPLC (see above conditions) showed 97% purity.
Beta-(2,4-diaminopyrimido [4,5,-β]pyrazin-6-yl-alphaethyl-5-ethylthiophene-2-carboxylic Acid (III-Sb)
A solution of the dicarboxylic acid III-7b (0.22 g, 0.57 mmol) in dry dimethylsulfoxide (10 mL) was heated to 125° C. for 30 minutes. The amber solution was then concentrated under high vacuum, and the residue was washed thoroughly with ether, then suspended in water (10 mL). Sufficient ammonium hydroxide was added to bring about solution, then adjusted to pH 5 with hydrochloric acid and filtered. The resulting tan solid was washed with water, then dried in vacuo, yielding 0.14 g (70%).
HPLC indicated 90.5% purity. Analysis gave the following results. UV (0.1N NaOH) 256 nm (28.546), 372 (7,300). Mass spectrum (DC1-NH 3 ) 561 (TMS 3 )=345 (M+H). Anal Calcd for C 15 H 16 N 6 O 2 S . 0.6 H 2 O: C, 50.72%; H, 4 88%; N, 23.66% Found: C, 50.54%; H, 4 94%; N 23 91%.
N-[alpha-Ethyl-beta-(2,4-diamino-[4,5-β]-pyrazin-6-yl)-5-ethyl-2-thenoyl-glutamic Acid Diethyl Ester (III-9b)
A mixture of the carboxylic acid III-Sb (0.99 g, 2.9 mmol) and triethylamine (2.7 g, 26.7 mmol) in dry N,N-dimethylformamide (50 ml) was stirred at room temperature for 1 hour, then treated with isobutyl chloroformate (0.81 g, 5.9 mmol). The mixture was stirred for 1 hour, treated with L-glutamic acid diethyl ester hydrochloride (1.42 g, 5.9 mmol), and stirred at room temperature for 2 hours. Isobutyl chloroformate (0.41 g, 3.0 mmol) was added and the mixture was stirred at room temperature for 1 hour. L-glutamic acid diethyl ester hydrochloride (0.72 g, 3.0 mmol) was added and the mixture was stirred at room temperature for 1 hour. Isobutyl chloroformate (0.41 g, 3.0 mmol) was added and the mixture was stirred for 1 hour. L-glutamic acid diethyl ester hydrochloride (0.42 g, 3.0 mmol) was added and the reaction mixture was stirred at room temperature for 16 hours. The mixture was concentrated under high vacuum. The yellow solid was washed with water then dried in vacuo. Chromatography on flash silica gel (2% methanol in chloroform eluent) gave the product III-9a as a yellow foam in 20% yield (0.3g). Analysis gave the following results.
NMR (CDCl 3 ): delta =0.90 (t, 3 H C,0-CH 2 -CH 3 ); 1.30 (m, 6 H, 2 X OCHC 2 CH 3 ); 2.17 (m, 2 hours, glu C 3 -H 2 ); 2.47 (m, 2 hours, glu C 4 -H 2 ); 3.20 (m, 3 H, C 9 -H2+C 10 -H); 4.16 (m, 4 H, 2 X OCH 2 ); 4.75 (m, 1 hour, CHNH); 5.45 (broad s, NH); 6.55 (m, 1 hour, C 3 -H); 6.95 (m, 1 hour, NHCH); 7.30 (d, 1 hour, C 4 -H); 8.41 (d, 1 hour, CTH). Anal. Calcd. for C 24 H 31 N 7 O 5 S . 0.7 H 2 O: C, 53.16%; H, 5.93%; N, 18.08; Found: C, 53.43%; H, 5.79; N, 17.73%.
N-[alpha-Ethyl-beta-(2,4-diamino-[4,5-β]-pyrazin-6-yl)-5-ethylthiophene-2-carbonyl]-glutamic Acid (III-10b, Compound No. 6)
A solution of the diester III-9b (0.55 mmol) in 2-methoxyethanol (10 ml) was treated with 10% sodium hydroxide (5 ml) and water (5 ml). After stirring for 75 minutes the solution was neutralized to pH 5 with 2M hydrochloric acid and concentrated under high vacuum. The residue was treated with water and the mixture filtered. The yellow solid was dried in vacuo, yielding 0.15 g (57%) of product III-10b.
HPLC 96.9% purity. Analysis gave the following results. UV (0.1 N, NaoH) 256 nm (28, 139), 371 (6, 810); mass spectrum m/e 762 (TMS 4 M+H).
EXAMPLE 6
10-Allyl-10-Deazaaminopterin
This example illustrates a preparation of 10-allyl-10-deazaaminopterins according to procedure illustrated in the Reaction Scheme 4.
α-Allylhomoterephthalic Acid Dimethyl Ester (IV-1a)
A mixture of 35% potassium hydride oil suspension (6.04 g, 35% w/w/, 53 mmols of potassium hydride) in 240 mL of sieve dried tetrahydrofuran was cooled to 0° C. The cold mixture was treated with homoterephthalic acid dimethyl ester (10.0 g, 48 mmols). The mixture was stirred at 0° C. for one hour. Allyl bromide (6.41 g, 53 mmols) was added and the mixture was stirred at 0° C. for 30 minutes, then at room temperature for 16 hours. The resulting mixture was treated with 4.8 mL of 50% acetic acid, then poured into 480 mL of water. The mixture was extracted with ether (2 ×250 mL). The ether extracts were combined, dried over magnesium sulfate, and concentrated to a brown oil. Chromatography on 250 g of flash silica gel (10% ether in hexane eluent) gave the product IV-1a as a pale yellow oil, 10.5 g (89% yield).
1 H NMR (CdCl 3 ): delta 7.69 (q, 4H, Ar); 5.64 (m, 1H, CH═CH 2 ; 5.09 (m, 2H, CH 2 ═CH); 3.80 (m, 7H, 2 x CH 3 O/ArCH); 2.75 (m, 2H, CH 2 CHAr).
10-Allyl-10-carbomethoxy-4-deoxy-4-amino-10-deazapteroic Acid Methyl Ester (IV -2a).
A mixture of potassium hydride in oil (2.43 g, 35% w/w, 21.2 mmols) in dry dimethylformamide (25ml) was cooled to -5° C. The cold mixture was treated, dropwise, with a solution of α-allylhomoterephthalic acid dimethyl ester (IV-la) (5.25 g, 21.2 mmols) in dry dimethylformamide (25 ml) then stirred at 0° C. for 45 minutes. After cooling to -20° C., a solution of 2,4-diamino-6-bromomethylpteridine hydrobromide 0.2 isopropanol (2.45 g, 7.06 mmols) in dry dimethylformamide (40 ml) was added dropwise, maintaining a -20° C. reaction temperature. The temperature was allowed to rise to 20° C. and was stirred for 2.5 hours. The reaction was then adjusted to pH 8 by addition of solid carbon dioxide. Concentration under high vacuum gave a residue which was dissolved in chloroform. This solution was washed with water, dried, and concentrated. The residue was washed with ether and dried in vacuo giving 2.2 g (74% yield) of product IV-2a.
Thin layer chromatography (10% methanol in chloroform on silica gel plates) showed a single spot, Rf 0.4. Mass spectrum m/e 423 (M / H). 1 H NMR (CdCl 3 ): delta 8.45 (s, 1H, 7-H), 8.03 (d, 2H, C 6 H 4 ), 7.37 (d, 2H, C 6 H 4 ), 5.50 (m, CH═CH 2 ), 4.95 (m, 2H, CH 2 ═CH), 3.90 (s, 3H, ArCOOCH 3 ), 3.60 (m, 5H, C-10 COOCH 3 - C-9 CH 2 ), 2.83 (m, 2H, CH 2 CH═CH 2 ).
10-Allyl-10-carboxy-4-deoxy-4-amino-10-deazapteroic Acid (IIIa)
A solution of the dimethyl ester (IV-2a) (2.0 g, 4.7 mmols) in 2-methoxyethanol (2 ml) was treated with water (2 ml) then 10% sodium hydroxide (2 ml). The solution was stirred at room temperature for 24 hours. The solution was adjusted to pH 6 with acetic acid and concentrated under high vacuum to give a residue which was then dissolved in water (10 ml). Further acidification to pH 3 resulted in a precipitate which was collected, washed with water and dried in vacuo to yield 1.53 g (81%) of yellow solid product IV-3a.
HPLC indicated 90% purity. Mass spectrum m/e 395 (M+H); UV (0.1N NaOH): π max 255 nm (28,194), 368 (7,444).
10-Allyl-4-deoxy-4-amino-10-deazapteroic Acid/IV-4a)
A solution of the dicarboxylic acid (IV-3a) (0.26 g) in dry dimethyl sulfoxide (10 ml) was placed in a preheated 142° C. oil bath for 10 minutes. The solution was cooled to 35° C. and concentrated under high vacuum. The residue was triturated with ether to yield a tan solid, 0.23 g, 99% yield of product IV-4a.
HPLC indicated 95% purity. Mass spectrum m/e 351 (M+H).
10-Allyl-10-Deazaaminopterin Diethyl Ester (IV-5a)
A solution of the acid (IV-4a) (0.87 g, 2.5 mmols) in dry dimethyl formamide (25 ml) was treated with triethylamine (1.4 ml, 1.01 g, 9.96 mmols). After stirring at room temperature for 20 minutes, the solution was treated with isobutyl chloroformate (0.5 ml, 0.53 g, 3.9 mmols). The mixture was stirred at room temperature for one hour then treated with L-glutamic acid diethyl ester hydrochloride (0.96 g, 4.0 mmols). After stirring for 1.5 hours isobutyl chloroformate (0.5 ml) was again added. The mixture was stirred for one hour, then again treated with L-glutamic acid diethyl ester hydrochloride (0.96 g). After 1.5 hours, the process was repeated with isobutyl chloroformate (0.5 ml) and L-glutamic acid diethyl ester hydrochloride (0.96 g) and the final mixture stirred at room temperature for 16 hours. The reaction mixture was concentrated under high vacuum and the residue dissolved in chloroform, washed with water, then saturated with sodium bicarbonate. The organic layer was dried over magnesium sulfate and concentrated in vacuo. The residue was chromatographed on flash silica gel (2% methanol in chloroform) to yield a pure product IV-5a in 30% yield as shown by thin layer chromatography (10% methanol in chloroform on silica gel plates).
1 H NMR (CdCl 3 ):68.40 (s, 1H, 7-H), 7.75 (m, 2H, C 6 H 4 ), 5.63 (m, 1H, CH═CH 2 , 4.15 (m, 5H, 2 x CH 2 CH 3 /CHN), 3.20 (m, 3H, 9-H 2 /10-H), 2.20 (m, 6H, CH 2 CH═CH 2 / glu 3-H 2 /glu 4-H 2 ), 1.25 (m, 6H, 2 x CH 3 CH 2 ),
10-Allyl-10-deazaaminopterin/IV-6a)
The diethyl ester (IV-5a) (0.3 g, 0.56 mmols) was dissolved in 2-methoxyethanol (3 ml) and the solution was treated with water (3 ml) then 10% sodium hydroxide (3 ml). The solution was stirred for one hour at room temperature. The reaction mixture was neutralized to pH 5 with acetic acid. Concentration under high vacuum gave a residue which was dissolved in water (5 ml). Further adjustment to pH 3 gave a precipitate which was collected. The tan solid was washed with water and dried in vacuo giving 0.10 g (37%) of product IV-6a.
Mass spectrum m/e 489 (M+H). UV (0.1N NaOH) λ max 255 (27,330), 371 (6403); HPLC indicated 94% purity.
EXAMPLE 7
10-Proparqyl-10-Deazaaminopterin
This example illustrates a preparation of 10-propargyl-10-deazaaminopterin compound IV-6b according to procedure illustrated in the Reaction Scheme 4.
α-Propargylhomoterephthalic Acid Dimethyl Ester (IV-1b)
A mixture of 35% potassium hydride in oil (6.04 g, 35% w/w, 53 mmols of potassium hydride) in 240 mL of sieve dried tetrahydrofuran was cooled to 0° C. The cold mixture was treated with homoterephthalic acid dimethyl ester (10.0 g, 48 mmols). The mixture was stirred at 0° C. for one hour. Propargyl bromide (53 mmols) was added and the mixture stirred at 0° C. for 30 minutes, then at room temperature for 16 hours. The resulting mixture was treated with 4.8 mL of 50% acetic acid, then poured into 480 mL of water. The mixture was extracted with ether (2×250 mL). The ether extracts were combined, dried over magnesium sulfate, and concentrated to a brown oil. Chromatography on 250 g of flash silica gel (10% ether in hexane eluent) gave the product IV-1b as a white solid mp 63°-65° C.
Mass spectrum m/e 247 (M+H). IR (nujol C.tbd.C-H, 3268 cm -1 . -1 H NMR (CDCl 3 ):68.05 (d, 2H, C 6 H 4 ), 7.40 (d, 2H, C 6 H 4 ), 3.91 (s, 3H, ArCOOCH 3 ), 3.88 (dd, 1H, ARCH), 3.71 (s 3H, --CHCOOCH 3 ), 2.95 (dddd, 1H, CH 2 ), 2.64 (dddd, 1H, CH 2 ), 1.96 (dd, 1H, C.tbd.CH). Anal. Calcd, for C 14 H14O 4 : C, 68.3; H, 5.73. Found: C, 68.0; H, 5.60.
10-Proparqyl-10-carbomethoxy-4-deoxy-4-amino-10-deazapteroic Acid Methyl Ester (IV-2b)
A mixture of potassium hydride (2.43 g, 35% w/w, 21.2 mmols) in dry dimethylformamide (25 ml) was cooled to -5° C. The cold mixture was treated, dropwise, with a solution of propargylhomoterephthalic acid dimethyl ester (IV-1b) (21.2 mmols) in dry dimethylformamide (25ml), then stirred at 0° C. for 45 minutes. After cooling to -20° C., a solution of 2,4- diamino-6-bromomethylpteridine hydrobromide 0.2 isopropanol (2.45 g, 7.06 mmols) in dry dimethylformamide (40 ml) was added, dropwise, maintaining a -20° C. reaction temperature. The temperature was allowed to rise to 20° C. and was stirred for 2.5 hours. The reaction was then adjusted to pH 8 by addition of solid carbon dioxide. Concentration under high vacuum gave a residue which, however, was not soluble in common organic solvents, and was therefore carried unpurified into the next step. The purity was acceptable by thin layer chromatographic analysis. The crude weight recovery of the product IV-2b was 90%. Mass spectrum m/e 420.
10-Propargyl-10-carboxy-4-deoxy-4-amino-10-deazapteroic Acid (IV-3b)
A solution of the dimethyl ester (IV-2b) (4.7 mmols) in 2-methoxyethanol (2 ml) was treated with water (2 ml) then 10% sodium hydroxide (2 ml). The solution was stirred at room temperature for 24 hours. The solution was adjusted to pH 7-8 with acetic acid and concentrated under high vacuum to give a residue which was then dissolved in water (10 ml). Further acidification to pH 6 resulted in a precipitate which was collected, washed with water and dried in vacuo. HPLC analysis indicated 92% purity after re-precipitation of the product from basic solution. The product IV-3b was obtained as a white solid in 75% yield.
Mass spectrum m/e 680 (M+H as the TMS 4 derivative).
10-Proparqyl-4-deoxy-4-amino-10-deazapteroic Acid (IV-4b)
Three decarboxylations of IV-3b were conducted on 86, 86, and 55 mg of material. In each case the reaction aliquot was dissolved in 3 ml of dimethyl sulfoxide and immersed for a period of five minutes in an oil bath preheated to 123° C. The reactions were combined and the solvent removed in high vacuum. The residue was precipitated twice from dilute ammonium hydroxide solution by addition of acetic acid. HPLC analysis indicated 85% purity with no impurity exceeding 4%. The product IV-4b was a tan solid (29% yield). Mass spectrum 564 (M+H as the TMS 3 derivative).
10-Propargyl-10-deazaminopterin Diethyl Ester (IV-5b)
A solution of the acid (IV-4b) (0.87 g, 2.5 mmols) in dry dimethyl formamide (25 ml ) was treated with triethylamine (1.4 ml, 1.01 g, 9.96 mmols). After stirring at room temperature for 20 minutes, the solution was treated with isobutyl chloroformate (0.5 ml, 0.53 g, 3.9 mmols). The mixture was stirred at room temperature for one hour then treated with L-glutamic acid diethyl ester hydrochloride (0.96 g). After 1.5 hours the process was repeated with isobutyl chloroformate (0.5 ml ) and L-glutamic acid diethyl ester hydrochloride (0.96 g) and the final mixture stirred at room temperature for 16 hours. The reaction was concentrated under high vacuum and the residue dissolved in chloroform, washed with water, then with saturated sodium bicarbonate. The organic layer was dried over magnesium sulfate and concentrated in vacuo. The residue was chromatographed on flash silica gel (2% methanol in chloroform).
Following chromatography, an aliquot was saponified. HPLC analysis indicated 93% purity. The product IV-5b was obtained in a yellow foam in 55% yield. Mass spectrum m/e 534 (M+H) . 1 H NMR (CdCl 3 ): delta 8.5 (s, 1h 7-H), 7.75 (d, 2H, C 6 H 4 ), 7.28 (d, 2H, C 6 H 4 ), 7.0 (br s, 1H, NH), 5.35 (br s, 1H, NH), 4.77 (m, 1H, NHCH), 4.10 and 4.25 (q, 4H, OCH 2 ), 3.46 (m, 2H, C-9CH 2 ), 3.23 (m, 1H, C-10H), 2.62 (m, 2H, C.tbd.CCH 2 ), 2.46 (m, 2H, CH 2 COOEt), 2.15 and 2.32 (m, 2H, glu-3CH 2 ), 2.04 (brS, 1H, C.tbd.CH), 1.33 and 1.29 (t, 6H, CH 2 CH 3 ).
10-Propargyl-10-deazaminopterin (VI-6b)
The diethyl ester (IV-Sb) (0.3 g, 0.56 mmols) was dissolved in 2-methoxyethanol (3ml) and the solution was treated with water (3 ml) then 10% sodium hydroxide (3 ml). The solution was stirred for one hour at room temperature. The reaction mixture was neutralized to pH 5 with acetic acid. Concentration under high vacuum gave a residue which dissolved in water (5 ml). Further adjustment to pH 3 gave a precipitate which was collected. The product IV-6b was obtained as a pale yellow solid in 72% yield.
HPLC analysis indicated 95% purity. Mass spectrum m/e 765 (as the TMS3 derivative). UV (0.1N NaOH) 2max 256 (ε29,800), 372 (ε7000). Anal. Calcd for C 23 H 23 N 7 O 5 H 2 O C, 52.9; H, 5.40; N, 18.8. Found: C, 52.8, H, 5.17; N, 18.4.
EXAMPLE 8
Tablet Formulation
This example illustrates preparation of compounds of the current invention in a tablet form.
______________________________________Composition mg/Tablet______________________________________Heteroaroyl-10-deazaaminopterin 15Lactose 86Cornstarch (dried) 45.5Gelatin 2.5Magnesium stearate 1.0______________________________________
The method of preparation is identical with that of Example 1, except that 60 mg of starch is used in the granulation process and 20 mg during tableting.
Using the same procedure, 10-alkynyl and 10-alkenyldeazaaminopterins are formulated as tablets.
EXAMPLE 10
Capsule Formulation
This example illustrates preparation of compounds of the current invention in a capsule form.
______________________________________Capsule Composition mg/Capsule______________________________________Heteroaroyl-10-deazaaminopterin 250Lactose 150______________________________________
The heteroaroyl-10-deazaaminopterin compound and lactose are passed through a sieve and the powders well mixed together before filling into hard gelatin capsules of suitable size, so that each capsule contains 400 mg of mixed powders.
Using the same procedure, 10-alkynyl and 10-alkenyldeazaaminopterins are formulated as capsules.
EXAMPLE 11
Suppositories
This example illustrates preparation of compounds of the current form as suppositories.
______________________________________Composition mg/suppository______________________________________Heteroaroyl-10-deazaaminopterin 50Oil of theobroma 950______________________________________
The heteroaroyl-10-deazaaminopterin compound is powdered and passed through a sieve and triturated with molten oil of theobroma at 45° C. to form a smooth suspension.
The mixture is well stirred and poured into molds, each of nominal 1 g capacity, to product suppositories.
Using the same procedure, 10-alkynyl and 10-alkenyldeazaaminopterins are formulated as cachets.
EXAMPLE 12
10-Deazaaminopterins Formulated as Cachets
This example illustrates formulation of compounds of the current invention into cachets.
______________________________________Composition mg/Cachet______________________________________Heteroaroyl-10-deazaaminopterinLactose 400______________________________________
The heteroaroyl-10-deazaaminopterin compound is passed through a mesh sieve, mixed with lactose previously sieved and fitted into cachets of suitable size so that each contains 500 mg.
Using the same procedure, 10-alkynyl-10-alkenyldiazaaminopterins are formulated as tablets.
EXAMPLE 13
This example illustrates a preparation of compounds of the current invention in injection forms.
______________________________________Composition Intramuscular injection mg/Injection______________________________________Heteroaroyl-10-deazaaminopterin 10Sodium carboxymethylcellulose 2.0Methyl paralpha-hydroxybenzoate 1.5Propyl para-hydroxylbenzoate 0.2Water for injection to 1.0 ml______________________________________
Other injection forms such as intraperitoneal, intravenous subcutaneous are prepared similarly.
The compound of the invention and the other excipients, listed above, were dissolved in a sterile solution in an aqueous carrier system. Using the same procedure, 10-alkynyl, and 10-alkenyl-deazaaminopterins are formulated as injections.
EXAMPLE 14
Antiarthritic effect of Heteroaroyl-10-Deazaaminopterin in Mammals
This example illustrates the antiarthritic activity of the compounds of the current invention in mammals.
The study used a mouse model of inflammatory disease that occurs in response to an antigenic challenge with Type II collagen according to method described in Nature, 283, 666-668 (1890).
DBA/1 mice were immunized with a suspension of fetal bovine Type II collagen (1 mg/ml) prepared in complete Freund's adjuvant. The primary injection was given using 0.1 ml of the collagen emulsion giving a total of 0.1 mg of Type II collagen per mouse. The animals were given a booster injection of Type II collagen (100 μg in 0.01M acetic acid) on day 21 by intraperitoneal injection.
The results of the in vivo testing of methotrexate showed that using prophylactic regimens in which drug administration was initiated two days prior to administration of antigen (Type II collagen) was more effective than starting drug at day 19, two days prior to the first and only boost with Type II collagen. In this model the untreated positive control animals have an incidence of arthritis ranging from 90% to 100% of injected animals at day 44.
The effect of methotrexate and test compounds on the extent of inflammation was determined by visual observation and by direct analysis of paw swelling using caliper measurements. The results are summarized in Table II, and show a direct correlation between the decrease in the number of animals having disease and a decrease in the extent of inflammation, as determined by paw swelling.
The following data illustrate administration to mice of compounds 1,2,5,and 6 of Table 1, of the invention and 10-allyl-10-deazaminopterin and the effect compared to the known antiarthritic drug methotrexate in the evaluation of the compounds antiinflammatory activity. The data are presented as two separate measurements: the visually observed presence of inflammation in the mouse, and the caliper-measured degree of swelling of the rear paws of the mouse.
TABLE 2__________________________________________________________________________ No mice affected Avg. thickness of on day indicated.sup.b rear paws (mm) over Dose Day Day Day days 30-44.sup.cCompound mg/kg 30 37 44 Treated Untreated__________________________________________________________________________None 31/43 38/43 41/43 2.29-2.73 1 R = H 18.0 0/8 1/8 2/8 2.14-2.38 X = 2 R = C.sub.2 H.sub.5 15.0 0/8 1/8 1/8 2.15-2.26 X = 5 R = H 8.0 3/8 2/8 4/8 2.22-2.33 X = 6 R = C.sub.2 H.sub.5 2.5 2/8 6/8 6/8 2.18-2.75 X =10 10-Allyl-10- 12 1/8 5/8 4/8 2.19-2.35deazaminopterinMTX.sup.a 9.0 1/22 1/22 6/22 2.18-2.34__________________________________________________________________________ .sup.a MTX and untreated controls are composites from multiple runs. .sup.b Visual evidence of inflammation. .sup.c Values in parentheses are 30 day and 44 day measurements vs. equivalent for untreated controls; decrease in inflammation vs. control i most notable at day 44.
It is apparent from the above results that the number of test mice affected was considerably decreased by administration of the heteroaroyl-10-deazaaminopterin compound. The results show that heteroaroyl-10-deazaaminopterin compounds on a similar dosage level are at least as effective as methotrexate. The antiinflammatory activity of methotrexate is accepted as an effective comparative standard for determination of the antiinflammatory activity of other compounds. Therefore, the heteroaroyl-10-deazaaminopterins compounds are expected to be at least as effective as methotrexate, under similar conditions. The potent anti-arthritic activity of the heteroaroyl-10-deazaaminopterin compounds tested is evident from the results.
EXAMPLE 15
Effect of 10-Proparqyl-10-Deazaaminopterin on Murine Leukemia Cells
This example illustrates the evaluation of the effect of 10-propargyl-10-deazaaminopterin on growth inhibition of L 1210 murine leukemia cells in culture and for its ability to inhibit dihydrofolate reductase derived from L 1210 cells.
The used method was that described in Biochem. Pharmacol., 28:2993-2997 (1973). Enzyme was derived from L 1210 murine leukemia cells. The inhibition was conducted at pH 7.3. Data were analyzed according to the method described in Biochem J. 135:101-107 (1973). Methotrexate was used as a control.
Murine L1210 cells were obtained as intraperitoneal ascites suspensions from BD2F 1 mice. The cells were grown in RPM1 1640 medium supplemented with 10% fetal calf serum. Cultures in the logarithmic stage of growth were harvested, resuspended and exposed to test compounds at varying concentrations. Growth of controls was monitored to verify that the growth pattern was normal. At 72 hours, cell counts were taken and averaged and the means were plotted against drug concentration to determine the concentration causing 50% inhibition of cell growth.
In one set of studies, the effect of 10-allyl and 10- propargyl-10-deazaaminopterins on growth inhibition of L1210 leukemia cells was determined and compared with the effect of methotrexate. Results are shown in Table 3.
TABLE 3______________________________________ L/1210 GrowthCompound Inhibition IC.sub.50 nM______________________________________10-Allyl-10-deazaminopterin 4.3010-Propargyl-10-deazaminopterin 2.0Methotrexate 9.5______________________________________
As seen from the Table 3, under these circumstances, 10-propargyl-10-deazaaminopterin was more than 4.5 times as effective in inhibiting the growth of L1210 leukemia cells than methothrexate and more than twice as active than corresponding 10-allyl-10-deazaminopterin.
When the effect of 10-propargyl-10-deazaaminopterin on the inhibition of dihydrofolate reductase derived from 1210 leukemia cells was studied, as shown in Table 4, it was found to be one-third as potent as MTX for enzyme inhibition. This was consistent with extension of chain length beyond two carbon units. However, as seen above, the propargyl compound was nearly 5-fold more potent than MTX as an inhibitor of growth in L1210 cells. This result prompted a measurement of the transport properties for facilitated entry into the L1210 cells vs MTX. As seen from Table 4, 10-fold transport advantage vs MTX for influx K 1 was observed as determined by competitive binding for the transport protein.
TABLE 4______________________________________ DHFR Growth Transport Inhibn: Inhibn: Influx:Compound (K.sup.i) IC.sub.50, μM.sup.b K.sub.i, μM.sup.b______________________________________IV-6b 10-Propargyl-10-DA 18.2 ± 4.0 2.0 0.45 ± 0.1MTX 5.75 ± 1.0 9.50 4.2 ± 0.5______________________________________
EXAMPLE 16
Antitumorigenic Effect of 10-Propargyl-10-Deazaaminopterin
This example illustrates the effect of 10-propargyl-10-deazaaminopterin in suppression of the tumor growth.
The propargyl compound was evaluated in the EO771 murine mammary tumor model in vivo according to method described in Proc. Ann. Soc. Clin. Oncol., 11:51 (1992)
Tumor evaluation was performed in EO771 solid subcutaneous mammary tumor in BDF1 female mice. The mice were injected with tested compound on the third day post tumor development with doses as indicated in Table 4.
At a dose of 36 mg/kg compound IV-6b totally suppressed the growth of the tumor at the 14 and 21 day post treatment points. The compound was also effective at a 24 mg/kg dose at day 14, but some regrowth had commenced by day 21. At the 36-mg dose one completely tumor-free survivor was noted among the surviving animals. Methotrexate was not as effective in this assay at day 21 even at a dose of 9 mg/kg. This assay is indicative that compounds of this invention and their analogues are effective in suppression of the neoplastic growth. The EO771 solid tumor model is somewhat predictive for activity in human breast cancer as demonstrated by 10-ethyl-10-deazaminopterin (Edatrexate). This drug was highly effective in EO771 and has shown outstanding efficacy in the clinic with late-stage breast cancer.
TABLE 5______________________________________E0771 Solid Mammary Tumor Evaluation in BDF1 Female Mice.sup.a Average tumor vol (mm.sup.3)Dose No. day 10(mg/kg).sup.b mice (% T/C) 14 21______________________________________Control 5 131 (100) 1232 (100) 2066 (100)IV-6b (24) 3 62 (47) 19 (2) 204 (100)IV-6b (36) 3 48 (31) 6 (1) 21 (1).sup.cMTX (3) 5 113 (86) 187 (15) 1260 (61)MTX (6) 5 34 (26) 19 (2) 382 (18)MTX (9) 5 4 (3) 19 (2) 310 (15)______________________________________ .sup.a Subcutaneous tumor. .sup.b Dose schedule day 3, QDX 5 (ip). .sup.c One mouse was tumor free of two survivors.
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There is disclosed certain heteroaroyl 10-deazaaminopterin and 5, 10 and 8, 10 di deazaminopterin compounds and their use for treatment of rheumatoid arthritis and related diseases and preparative process.
Also disclosed are 10 alkenyl-(and alkynyl) 10-deazaminopterins also disclosed for treatment of rheumatoid arthritis and for leukemia and ascites tumors and preparative process.
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BACKGROUND OF THE INVENTION
The present invention relates to a novel sintered body suitable for use as a refractory or abrasive material with its high mechanical strengths at elevated temperatures.
In the prior art, various kinds of sintered bodies are employed for manufacturing certain structural materials suitable for use for rocket housings, turbine blades, high-speed cutting tools and the like, in which high mechanical strengths, e.g. flexural strength and hardness, are essential even at extremely high temperatures. As is well known, a class of such sintered bodies is composed of titanium diboride (TiB 2 ) as the basic component utilizing its high melting point, hardness and mechanical strengths at elevated temperatures. These TiB 2 -based sintered bodies are usually prepared by sintering a binary powder mixture composed of TiB 2 as the main component and a second component including a powder of a metal such as chromium, molybdenum, rhenium and the like, a metal diboride such as chromium diboride (CrB 2 ), Zirconium diboride (ZrB 2 ) and the like, and a nickel phosphide or a nickel-phosphorus alloy (hereinafter denoted as Ni.P).
The above described binary sintered bodies, however, have their respective drawbacks in their performance as well as in their preparation. For example, an extremely high sintering temperature of 2000° C. or higher is required for the sintering of the TiB 2 -metal, e.g. TiB 2 -chromium, TiB 2 -molybdenum and TiB 2 -rhenium, binary sintered bodies giving rise to a very hard difficulty in the production of industrial scale. In addition, these TiB 2 -metal binary sintered bodies suffer from their relatively low flexural strengths in the range of, for example, 40-50 kg/mm 2 . The TiB 2 -metal diboride, e.g. TiB 2 -chromium diboride and TiB 2 -zirconium diboride, binary sintered bodies are also subject to the drawbacks of the high sintering temperature and the relatively low flexural strength along with the low relative density, i.e. the ratio of the apparent density to the true density of the sintered body.
The sintering temperature of the TiB 2 -Ni.P binary sintered body, on the other hand, may be as low as ranging from 1000° to 1600° C. and a satisfactorily high flexural strength of around 100 kg/mm 2 is readily obtained with these binary sintered bodies (see, for example, Japanese Patent Disclosure No. SHO 52-106306). The binary sintered bodies of this class have, however, rather poor heat resistance and cannot be used at a temperature exceeding the melting point of the Ni.P, viz. 890° C.
Thus, there have hitherto been known no satisfactory refractory or abrasive material which is a high-density, high-strength and heat-resistant sintered body of TiB 2 as the main component easily manufactured even with a not excessively high sintering temperature.
SUMMARY OF THE INVENTION
An object of the present invention is therefore to present a novel sintered body containing titanium diboride (TiB 2 ) as the main component and suitable for use as a high-temperature refractory material or an abrasive material with excellent mechanical strengths at an elevated temperature but obtained with a relatively low sintering temperature.
Another object of the present invention is to present a ternary sintered body composed of TiB 2 , Ni.P and a third component selected from the group consisting of metals of chromium, molybdenum, niobium, tantalum, hafnium, rhenium and aluminum as well as diborides thereof and a method for producing the same.
To be more specific, the Ni.P used in the present invention is an alloy of nickel and phosphorus containing 3 to 25% by weight of phosphorus based on nickel and the amount of Ni.P to be formulated in the ternary mixture is in the range of from 0.5 to 15 parts by weight per 100 parts by weight of TiB 2 and the amount of the third component is in the range of from 1 to 95 parts by weight per 100 parts by weight of TiB 2 .
The ternary sintered body of the invention is prepared by the techniques of hot-pressing under a pressure of 50-300 kg/cm 2 at a temperature of 1500°-2000° C. for 10-60 minutes or by sintering a green shaped body of the powder mixture under the above sintering conditions of temperature and time.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The base component of the inventive ternary sintered body as defined above is titanium diboride expressed by the chemical formula TiB 2 which is a well-known refractory material melting at 2980° C. and having a specific gravity of about 4.50 and a very high hardness suitable for use as an abrasive material. There is no specific limitation on the property of this TiB 2 insofar as a satisfactorily high purity is ensured. It is preferable that the TiB 2 has a particle size distribution as fine as possible in order to obtain a uniform blending with the other components.
The second component in the inventive ternary sintered body is a nickel phosphide or an alloy of nickel and phosphorus containing 3 to 25% or, preferably, 5 to 15% by weight of phosphorus based on the nickel content. This component may not necessarily be a ready-prepared Ni.P but, instead, powders of nickel metal and phosphorus can also be used in combination to be blended with the other components. The amount of Ni.P in the ternary mixture is in the range from 0.5 to 15 parts by weight per 100 parts by weight of the TiB 2 since smaller amounts than 0.5 parts by weight result in insufficient mechanical strengths while excessively high amounts over 15 parts by weight lead to a poorer heat resistance of the sintered body.
The third component is a powder of a certain metal exemplified by chromium, molybdenum, niobium, tantalum, hafnium, rhenium and aluminum or a diboride thereof, i.e. CrB 2 , MoB 2 , NbB 2 , TaB 2 , HfB 2 , ReB 2 or AlB 2 . These metal powders or metal borides may be used either singly or as a combination of two or more. The amount of this third component is in the range from 1 to 95 parts by weight per 100 parts by weight of the TiB 2 . It is recommended that, when this third component is a powder of the above named metals, the amount is limited to 1 to 10 parts by weight per 100 parts by weight of the TiB 2 while the metal borides are used preferably in an amount from 3 to 95 parts by weight per 100 parts by weight of the TiB 2 .
The ternary sintered body of the present invention is prepared by first blending the three components in fine powder forms intimately into a powder mixture with which a mold made of, for example, graphite is packed and subsequently sintering by the techniques of hot-pressing of the powder mixture is conducted in vacuum or in an atmosphere of a reducing gas such as hydrogen under a pressure of 50-300 kg/cm 2 at a temperature of 1500°-2000° C. for 10-60 minutes. Alternatively, a green body shaped by compression molding in advance with the above powder mixture is subsequently subjected to sintering in vacuum or in an atmosphere of a reducing gas at a temperature of 1500°-2000° C. to give a sintered body with almost identical properties as in the hot-pressing.
The combinations of the three components including the cases where the third component per se is a mixture of two or more of the metals or metal diborides are given below as to be exemplary:
TiB 2 -Ni.P-Cr; TiB 2 -Ni.P-Mo; TiB 2 -Ni.P-Ta; TiB 2 -Ni.P-Re; TiB 2 -Ni.P-Nb; TiB 2 -Ni.P-Mo-Ta; TiB 2 -Ni.P-Mo-Re; TiB 2 -Ni.P-Mo-Nb; TiB 2 -Ni.P-Ta-Re; TiB 2 -Ni.P-Ta-Nb; TiB 2 -Ni.P-Re-Nb; TiB 2 -Ni.P-Mo-Ta-Re-Nb; TiB 2 -Ni.P-CrB 2 ; TiB 2 -Ni.P-AlB 2 ; TiB 2 -Ni.P-TaB 2 ; TiB 2 -Ni.P-HfB 2 ; TiB 2 -Ni.P-CrB 2 -AlB 2 ; TiB 2 -Ni.P-CrB 2 -TaB 2 ; TiB 2 -Ni.P-CrB 2 -HfB 2 ; TiB 2 -Ni.P-AlB 2 -TaB 2 ; TiB 2 -Ni.P-AlB 2 -HfB 2 ; TiB 2 -Ni.P-TaB 2 -HfB 2 ; and TiB 2 -Ni.P-CrB 2 -AlB 2 -TaB 2 -HfB 2 .
The sintered bodies obtained with the above combinations of the components are excellent in the relative density, mechanical strengths, hardness and heat resistance and suitable as a refractory material and anti-abrasive material as well as a material for high-speed cutting tools.
Following are examples to illustrate the present invention in further detail. In the examples, parts are all given by parts by weight.
EXAMPLE 1 (EXPERIMENT NO. 1 TO NO. 5)
Ternary mixtures of TiB 2 , Ni.P and a powder of chromium metal in proportions as indicated in Table 1 below were each subjected to sintering by hot-pressing in a graphite mold in vacuum for 15 minutes with the conditions of the sintering temperature and pressure as shown in the table. The apparent density, flexural strength and Vickers hardness of these sintered bodies are set out in the table. The results were almost identical when sintering was carried out in an atmosphere of hydrogen gas.
TABLE 1__________________________________________________________________________Parts per100 parts Sintering Apparent Flexural Vickers hardness, kg/mm.sup.2,Exp. of TiB.sub.2 Temperature, Pressure, density, strength, at roomNo. Ni . P Cr °C. kg/cm.sup.2 g/cm.sup.3 kg/mm.sup.2 temperature at 1000° C.__________________________________________________________________________1 3 5 1700 120 4.58 70 2000 12002 3 5 1600 200 4.39 60 1800 a)3 3 5 1500 200 4.00 50 1600 a)4 1 9 1700 200 4.60 60 1750 b)5 1 9 1600 200 4.40 50 1600 b)__________________________________________________________________________ a) About 1/2 of the value at room temperature b) About 1/3 of the value at room temperature
EXAMPLE 2 (EXPERIMENT NO. 6)
The same powder mixture as used in Experiments No. 1 to No. 3 in Example 1 above was shaped into a green body by compression molding in cold and the shaped body was subjected subsequently to sintering by heating in vacuum at 1800° C. for 60 minutes. The thus obtained sintered body had an apparent density of 4.50 g/cm 3 , flexural strength of 60 kg/mm 2 , Vickers hardness at room temperature of 1750 kg/mm 2 and Vickers hardness at 1000° C. equal to about a half of the value at room temperature.
EXAMPLE 3 (EXPERIMENT NO. 7)
A ternary powder mixture composed of 100 parts of a TiB 2 powder, 1 part of Ni.P containing 8% by weight of phosphorus and 5 parts of a chromium diboride powder intimately blended was subjected to sintering by hot-pressing in a graphite mold in an atmosphere of hydrogen gas under a pressure of 165 kg/cm 2 at 1800° C. for 30 minutes. The resultant sintered body had a relative density of 99.9%, flexural strength of 75 kg/mm 2 , Vickers hardness at room temperature of 2500 kg/mm 2 and Vickers hardness at 1000° C. of 2000 kg/mm 2 . The results were almost identical when sintering was carried out in vacuum instead of hydrogen atmosphere.
EXAMPLE 4 (EXPERIMENTS NO. 8 TO NO. 23)
Powder mixtures each composed of 100 parts of TiB 2 , 1 part of Ni.P containing 8% by weight of phosphorus and one or more of metal borides selected from chromium diboride, aluminum diboride, tantalum diboride and hafnium diboride in amounts as indicated in Table 2 below were subjected to sintering by hot-pressing in the same manner as in the preceding example. Details of the preparation and the properties of the sintered bodies thus obtained are summarized in the table.
TABLE 2__________________________________________________________________________ Sintering Vickers hardness,Third Temper- Pres- Relative Flexural kg/mm.sup.2,Exp. component ature, sure, Atmos- density, strength, at roomNo. (parts) °C. kg/cm.sup.2 phere % kg/mm.sup.2 temperature at 1000° C.__________________________________________________________________________8 CrB.sub.2 (3) 1900 200 Vacuum 99.9 80 2600 22009.sup.(c) CrB.sub.2 (5) 2000 0 Vacuum 99.5 70 2400 200010 AlB.sub.2 (5) 1800 165 Vacuum 99.0 80 2200 175011 AlB.sub.2 (50) 1800 165 Vacuum 99.9 80 1800 130012.sup.(c) AlB.sub.2 (5) 2000 0 Vacuum 99.0 70 2100 170013 TaB.sub.2 (5) 1800 165 Vacuum 98.0 80 1800 135014 TaB.sub.2 (5) 1800 165 Hydrogen 98.0 75 1800 130015.sup.(c) TaB.sub.2 (5) 2000 0 Vacuum 99.0 75 1800 135016 HfB.sub.2 (5) 1800 165 Vacuum 99.5 80 1900 140017 CrB.sub.2 (5) + 1800 200 Vacuum 99.9 85 2100 1800 AlB.sub.2 (5)18 CrB.sub.2 (5) + 1800 200 Vacuum 99.9 80 2300 1700 TaB.sub.2 (5)19 CrB.sub.2 (5) + 1800 200 Vacuum 99.8 85 2400 1870 HfB.sub.2 (5)20 AlB.sub.2 (5) + 1800 200 Vacuum 99.8 83 2000 1660 TaB.sub.2 (5)21 AlB.sub.2 (5) + 1800 200 Vacuum 99.9 83 1800 1580 HfB.sub.2 (5)22 TaB.sub.2 (5) + 1800 200 Vacuum 99.9 85 1800 1470 HfB.sub.2 (5)23 CrB.sub.2 (5) + AlB.sub.2 (5) 1800 200 Vacuum 99.9 85 2000 1850 + TaB.sub.2 (5) + HfB.sub.2 (5)__________________________________________________________________________ .sup.(c) Green bodies shaped in advance by compressionmolding in cold wer sintered.
EXAMPLE 5 (EXPERIMENTS NO. 24 TO NO. 37)
Powder mixtures each composed of 100 parts of a TiB 2 powder, 1 part of the same Ni.P powder as used in Example 3 and one or more of metal powders selected from molybdenum, tantalum, niobium and rhenium in amounts as indicated in Table 3 below were subjected to sintering by hot-pressing under the conditions given in the table. The properties of the resultant sintered bodies are set out in the same table.
EXAMPLE 6 (EXPERIMENT NO. 38)
A powder mixture composed of 100 parts of a TiB 2 powder, 1 part of the same Ni.P powder as used in Example 3, 5 parts of a powder of chromium diboride and 5 parts of a powder of molybdenum metal intimately blended was subjected to sintering by hot-pressing in a graphite mold in vacuum under a pressure of 165 kg/cm 2 at 1800° C. for 30 minutes. The resultant sintered body had a relative density of 99.9%, flexural strength of 85 kg/mm 2 , Vickers hardness at room temperature of 2400 kg/mm 2 and Vickers hardness at 1000° C. of 1630 kg/mm 2 .
TABLE 3__________________________________________________________________________ Sintering Vickers hardness,Third Temper- Pres- Relative Flexural kg/mm.sup.2,Exp. component ature, sure, Atmos- density, strength, at roomNo. (parts) °C. kg/cm.sup.2 phere % kg/mm.sup.2 temperature at 1000° C.__________________________________________________________________________24 Mo(5) 1800 165 Hydrogen 99.9 81 2000 150025 Mo(3) 1900 200 Vacuum 99.9 80 2100 157026.sup.c) Mo(5) 2000 0 Vacuum 99.4 75 2000 150027 Ta(5) 1800 165 Vacuum 99.8 80 2000 135028 Re(5) 1800 165 Vacuum 99.7 80 2100 166029 Nb(5) 1800 165 Vacuum 99.8 80 2100 158030.sup.c) Re(5) 2000 0 Vacuum 99.7 75 2000 160031 Mo(3)+Ta(3) 1800 200 Vacuum 99.8 80 1900 130032 Mo(3)+Re(3) 1800 200 Vacuum 99.9 78 2000 133033 Ta(3)+Mo(3)+Nb(3) 1800 200 Vacuum 99.9 82 1880 137034 Ta(3)+Re(3) 1800 200 Vacuum 99.9 80 1850 122035 Ta(3)+Nb(3) 1800 200 Vacuum 99.6 80 1850 128036 Re(3)+Nb(3) 1800 200 Vacuum 99.8 83 1870 129037 Mo(2)+Ta(2) 1800 200 Vacuum 99.9 85 1800 1150 +Re(2)+Nb(2)__________________________________________________________________________ .sup.c) See footnote for Table 2.
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A novel sintered body suitable for use as a refractory or abrasive materials proposed with high mechanical strengths and hardness even at elevated temperatures. The sintered body of the invention is prepared by subjecting a powder mixture composed of titanium diboride as the base component, a nickel phosphide or nickel-phosphorus alloy and a third component selected from metals of chromium, molybdenum, niobium, tantalum, hafnium, rhenium and aluminum as well as diborides thereof, and the inventive sintered bodies are very advantageous in their industrial production owing to the relatively low sintering temperature of 2000° C. or lower and in their high performance at elevated temperatures to find wide applications in the fields of high-temperature engineering and as a material for the high-speed cutting tools.
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BACKGROUND OF THE INVENTION
[0001] Surfaces are often coated for esthetic and protective purposes. Typically, this coating is applied as a liquid that then dries (hardens) to a layer that beautifies and protects the underlying material. This liquid will be hereafter referred to as “paint”, but may be any type of permanent or semi-permanent coating applied as a liquid to a surface of any kind. The process of applying this coating is universally known as “painting” and a surface so coated as a “painted” surface.
[0002] The apparatus to be described is directed to maintaining the integrity of painted surfaces of buildings but also pertains to other types of painted surfaces, for example, vehicles and exterior furniture.
[0003] Afterwards the initial coating is complete, people and animals interact with the painted surfaces and often through carelessness or inadvertence, damage relatively small areas of the coated surfaces. Frequently after paint has been applied to a surface, a quantity of the paint remains. This leftover paint is useful for repainting the damaged areas.
[0004] It is the usual practice to keep the leftover paint in the original container and simply apply this paint with a brush, pad, or roller after damage occurs to a surface. However, this practice has numerous disadvantages. In the first place, the leftover paint more often than not occupies only a small fraction of the container. The paint may for this reason skin over or dry out because most of the volume in the container is air.
[0005] Secondly, paint is usually supplied in gallon containers, which inconveniently occupy a significant amount of shelf space. Third, the seal between the cover and the container itself may be compromised when paint dries in the sealing grooves during the painting process. Fourth, deteriorated paint must be replaced, and it is by no means certain that the replacement paint will match the original paint, and in any case it is expensive and inconvenient to do so. One can see that usual practice in this situation is problematic.
[0006] A number of solutions for this problem already exist. For example, U.S. Pat. No. 6,439,381 teaches individual storage containers for a number of different paints. '381 shows an applicator that must be attached to the container before touchup and then either cleaned or discarded after touchup is done.
[0007] U.S. Pat. No. 7,040,828 discloses a container for touchup paint having an applicator carried by a support that screws into the container. The user removes the applicator by unscrewing its support from the container. The applicator, having already been immersed in the paint, is instantly usable. The invention contemplates attaching the applicator to the container with a second thread set to prevent the paint in the container from drying while touching up occurs and to serve as a handle during the touchup process.
[0008] U.S. Pat. No. 7,338,227 discloses a system for mixing two parts for an epoxy paint and includes an applicator for touching up an existing coating.
[0009] Each of these designs solves the problem in some sense, but have disadvantages as well.
BRIEF DESCRIPTION OF THE INVENTION
[0010] An improved device for applying relatively small quantities of a liquid coating material such as paint comprises a container having an interior space defined by flexible walls, and having an opening for filling the interior space with a liquid coating material. This container opening has a first annular attachment feature. The first annular attachment feature preferably comprises relatively rigid threads encircling the container opening.
[0011] A coating material applicator has a porous applicator surface for receiving a liquid coating material. The applicator further comprises structure that distributes the coating material to the applicator surface.
[0012] An applicator support has a second annular attachment feature that can mate with the first annular attachment feature to form a seal opposing migration of liquid between the first and second annular attachment features. The applicator support also has an interior passage in flow communication with the applicator. When the second annular attachment feature is mated with the first annular attachment feature said applicator surface is in flow communication with the container's interior space.
[0013] A cap has an interior space sized to contain or enclose the applicator portion exterior to the container. The cap has an opening defined by a third annular attachment feature. The third annular attachment feature can mate with one or the other of the first and second annular attachment features to create a substantially airtight seal between them.
[0014] When the cap's third annular attachment feature is so mated with the one of the first and second annular attachment features, the cap's interior space holds the applicator. Little or no external air can reach the container interior space and the applicator, preventing paint held within the container and the applicator from hardening.
[0015] When touching up an area of the painted surface, the user squeezes the flexible walls of the container, reducing the internal space and forcing paint through the applicator from the first to the second applicator end portion. Liquid paint appears on the second end and may be then applied to the touchup area.
[0016] In one preferred version, the applicator comprises pliable, permeable, foam material. By squeezing the container walls, a user can force paint in the container through the applicator support and the applicator itself to the applicator surface. The coating material appears on the applicator surface, from which it may be transferred to a surface such as a wall. Releasing the container walls allow air exterior to the container to pass through at least a part of the applicator support to the container interior, replacing the volume of coating material previously applied and allowing the container walls to return to their unstressed (normal) shape.
[0017] In a second embodiment, the applicator support includes a tubular projection in flow communication with the applicator support's interior passage. The applicator includes a plenum mounted on and having an interior space in flow communication with the tubular projection. The plenum has a surface having an aperture therein and facing away from the tubular projection, and defining in part the plenum's interior space. A permeable fabric pad overlies the plenum's flat surface and the aperture therein to form the applicator surface.
[0018] In either embodiment, a vent in the applicator support can function to allow airflow to the container interior space.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a perspective view of a liquid coating material application device when in a “storage configuration.”
[0020] FIG. 2 . is an exploded perspective view of the liquid coating material application device, showing the various components thereof.
[0021] FIG. 3 is a perspective view of an alternate configuration for an applicator element of the liquid coating material application device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] Referring first to FIGS. 1 and 2 , the liquid coating material application device 10 shown therein provides the user with structure into which leftover paint or other liquid coating material may be place for later touch and repair use. Device 10 is intended for use with liquids such as paint that harden or dry when exposed to air for a period of time.
[0023] The exploded view of FIG. 2 discloses a container 15 having a mouth 37 and a longitudinal axis 18 . The walls of container 15 are flexible so that a typical user can compress them with hand force alone to reduce the volume of container 15 . A first annular attachment feature 31 encircles mouth 37 , and in a preferred embodiment comprises threads. Container 15 includes a relatively rigid tubular ring or band 16 defining mouth 37 into which the threads comprising a first annular attachment feature 31 may be molded.
[0024] An applicator support 41 has an interior passage allowing liquids to flow through support 41 generally along axis 18 . Support 41 in one preferred embodiment includes a tubular projection 25 in flow communication with this interior passage.
[0025] Support 41 includes a second annular attachment feature 28 shown here as threads encircling an opening of support 41 . Second annular attachment feature 28 is designed to mate with the threads comprising the first annular attachment feature 31 to attach support 41 to container 15 and form a seal opposing migration of liquid between the threads comprising the first and second annular attachment features 31 and 28 . FIG. 2 shows second annular attachment feature 28 structured to thread into the interior of container 15 .
[0026] A coating material applicator 20 in one version of this invention includes a plenum 22 carried by projection 25 . “Plenum” in the context here means a structure having an enclosed space in which liquid coating material can flow. Plenum 22 has an interior space in flow communication with projection 25 .
[0027] Plenum 22 includes a wall 27 facing away from projection 25 and defining at least a part of the plenum space. Wall 27 has at least one aperture 51 . A permeable fabric pad 54 on the wall 27 overlies aperture 51 . Preferably wall 27 is substantially rectangular and tilted with respect to axis 18 . Wall 27 and plenum 22 may be semi-rigid, resisting flexure, but also allowing some deflection of these components to conform to a wall surface.
[0028] Liquid coating material such as paint is poured into container 15 and then support 41 is threaded into container 15 . By tilting the assembly so that applicator 20 is below container 15 , and then squeezing the flexible walls of container 15 , liquid is forced through projection 25 and aperture 51 to soak pad 54 . Rubbing or dabbing pad 54 on a surface then applies the liquid to the surface.
[0029] The intent here is for a user to fill container 15 with leftover paint or other liquid coating material when an entire surface such as a wall is first coated. After filling container 15 , then applicator support 41 is mated with container 15 . First and second annular attachment features 31 and 28 form a seal preventing migration of air into the container 15 . However, air can migrate into container 15 through applicator 20 and applicator support 41 . This will cause the liquid within container 15 and applicator 20 to eventually harden and become worthless.
[0030] A cap 13 that encloses container 15 and applicator 20 will prevent deterioration of paint within them. Cap 13 has an interior space sized to contain applicator 20 and in this embodiment, fit around applicator support 41 as well. Cap 13 has an opening defined by a third annular attachment feature 19 , and in the preferred embodiment shown here comprises threads that mate with one of the other of the first and second annular attachment features 31 and 28 .
[0031] For example, first annular attachment feature 31 may comprise threads molded into the wall of container 15 that are engageable both for the interior and exterior of container 15 . In this embodiment, the configuration of the threads comprising third annular attachment feature 19 allow their mating with the exterior pattern of first annular attachment feature 31 on container 15 . Thus the threads comprising first annular attachment feature 31 mate with the second annular attachment feature 28 on the inside of container 15 and also mate with the third annular attachment feature 19 on the outside of container 15 .
[0032] The first and third annular attachment features 31 and 19 have a mating connection that forms a substantially airtight seal to prevent migration of air into the space between cap 13 and support 41 . The liquid material in container 15 and applicator 20 will not normally dry out or harden when exposed to such a small volume of air. Accordingly, the liquid may be suitable for use even years after attaching the cap 13 to container 15 using the first and third annular attachment features 31 and 19 .
[0033] It is likely that the smaller volume of air in intimate contact with the liquid material in container 15 and applicator 20 means that the shelf life of the material in container 15 will be longer than if left in a conventional can from which much of the coating material has already been removed and replaced with air.
[0034] Further experience may show that threads alone comprising mated annular attachment features 28 and 31 may not provide adequate sealing against migration of coating material from container 31 between them. Experience may also show that threads alone comprising mated annular attachment features 19 and 31 may not provide adequate sealing against migration of air between them into the internal space of cap 13 . In that case, an O-ring or other type of gasket may be necessary to provide the desired performance.
[0035] It is also possible that attachment features other than mated threads will serve to prevent air from entering the space that cap 13 encloses. For example, the caps that prevent felt tip markers from drying have a simple type of close-fitting detent that is substantially airtight. Note however, that the openings of these caps are typically only ½″ or in diameter. It may be true that such detent-type caps do not scale up effectively to a cap than may be 1-3″ in diameter, if for no other reason than attaching and detaching the cap requires too much strength.
[0036] In another design not currently preferred, the configuration of the threads comprising third annular attachment feature 19 allows their mating with the threads comprising second annular attachment feature 28 . In this case, the threads of second annular attachment feature 28 should extend axially along support 41 to an amount sufficient to allow engagement with third annular attachment feature 19 .
[0037] Typically after application and during use, a wall coating becomes damaged in only a few places. It is a great convenience for a user to simply remove cap 13 , squeeze the flexible walls of container 15 to force a suitable amount of liquid into applicator 20 for application to the damaged spots.
[0038] In the case of latex paint as the coating material, it may be helpful to simply run water over applicator 20 for a few seconds before attaching cap 13 . This removes and dilutes the paint within pad 54 and thereby lengthens the time that the paint remains usable.
[0039] Experience may show that air does not flow freely into container 15 through applicator 20 when releasing pressure on the walls of container 15 . If that is the case, vent hole 49 and closure flap 45 may allow airflow into container 15 . In the example shown, flap 45 is biased to move away from vent hole 49 . The user presses flap 45 against hole 48 when squeezing the container 15 walls to prevent liquid from seeping through hole 48 . Other types of vents such as self-closing vents may be usable as well.
[0040] FIG. 3 shows another embodiment have an alternate applicator support 41 ′ and applicator 36 , and is intended to thread directly into container 15 of FIG. 1 . Support 41 ′ comprises a hollow tube having threads 28 that will mate with the threads 37 of container 15 . Possibly the support 41 ′ and applicator 36 will be included in a commercial kit that also includes the components of FIG. 1 .
[0041] Applicator 36 comprises a permeable open cell foam block that fits closely within support 41 ′ and bonds to the interior walls thereof. The sidewall surface 38 of applicator 36 has a coating or layer substantially impervious to passage of coating material.
[0042] The end surface 34 of applicator 36 is preferably substantially flat and rectangular, and tilted with respect to axis 18 . Surface 34 must be permeable for the coating material, to allow coating material to flow to the surface. Surface 34 may have bristles 57 as shown or a permeable fabric surface to assist in applying the coating material to the surface to be coated, and to provide a desired texture of the final wall surface.
[0043] By squeezing the walls of container 15 when applicator support 41 ′ is mounted thereon, coating material is forced through applicator 36 to surface 34 . The coating material on surface 34 can then be applied to a surface as with the device of FIG. 1 . Sidewall 38 should be impervious to flow of coating material to properly channel coating material to surface 34 .
[0044] If experience shows that insufficient air can flow backwards through a fully saturated foam applicator 36 , a vent arrangement as shown in FIG. 2 may be necessary to allow replenishing air in container 15 .
[0045] When a particular project is complete, the user attaches cap 13 by mating the threads comprising annular attachment feature 19 and the outside of annular attachment feature 31 . If desired, a user may wish to rinse out applicator 36 partially or completely before attaching cap 13 .
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A device for touching up painted areas comprises a flexible container, and an applicator support connected to an opening of the container by threads or other attachment means. The applicator support carries an applicator for receiving paint or other coating material held in the container. The applicator is porous, allowing one to apply the paint to the painted areas in need of touch-up by squeezing the container. A cap having an interior space sized to contain the applicator can attach to the applicator support or container to enclose the applicator thereby creating a substantially airtight seal and preventing paint in the applicator and the container from drying out. By detaching the applicator support from the container, paint may be poured into the container.
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CROSS REFERENCE TO RELATED APPLICATIONS
Pursuant to 35 USC §120, this application claims the benefit of PCT/DE2006/001595 filed Sep. 12, 2006 which claims the benefit of German Patent Application No. 102005044330.3 filed Sep. 16, 2005. Each of these applications, is incorporated by reference in its entirety.
BACKGROUND
Like all other components, capacitors used in microelectronics must be further and further miniaturized in order to make correspondingly smaller, more energy-saving or merely more powerful terminal devices possible. For capacitors, dielectrics with relatively high dielectric constants can be used. Dielectric constants of more than 1000 can be achieved with ferroelectrics such as lead zirconate titanate (PZT), barium strontium titanate (BST), strontium titanate and others, depending on material and composition. When a voltage is applied to such ferroelectrics, piezoelectric behavior often appears in these materials, wherein the piezoelectric constant of these materials rises above 0.1 C/m 2 . In addition, the relative dielectric constant is usually likewise voltage-dependent. This opens the possibility of producing capacitors with ferroelectrics that are voltage-dependent or tunable by varying voltage.
Miniaturized capacitors and capacitors produced with thin-film technology can be structured as a plate, an interdigital, or a trench arrangement (pit capacitors). The highest capacitance densities, i.e. the highest capacitance of the thin-film capacitor per unit surface of the substrate material, are achieved with pit capacitors. These are difficult to manufacture, however. Plate capacitors with a dielectric layer arranged parallel to the substrate surface between two electrodes can achieve a capacitance density of up to 100 fF/μm 2 with the ferroelectric at a dielectric thickness of roughly 100 nm. A capacitor with a 10 pF capacitance then has a surface area of only 10×10 μm 2 .
Components constructed as plate capacitors in multilayer technology can achieve further increased capacitance densities, but are technologically more complicated. Interdigital capacitors, for which only one metal layer need be structured as an interdigital structure, are easy to manufacture. With a typical electrode spacing of roughly 500 nm, the capacitance densities that can be achieved are less than 1 fF/μm 2 . A capacitor with a 10 pF capacitance then has a surface area of more than 10×100 μm 2 .
SUMMARY
A disadvantageous effect of capacitors with piezoelectric behavior, and in particular with a voltage-dependent piezoelectric behavior, is the resulting variable quality factor curve at different frequencies. In certain frequency ranges capacitors with piezoelectric dielectrics display sharply reduced quality factors that can be traced back to acoustic resonances inside the capacitor structure. These resonances can strongly reduce the functionality of such components and make them unusable at frequencies which are generally rather high. These disadvantages have so far had the effect that high-capacitance capacitors have not been widely used in circuits and circuitry operating at mobile telephone frequencies.
The problem is therefore to specify a capacitor that is usable for HF applications and has a sufficient quality factor there.
It was found that the acoustic resonance frequencies of a piezoelectric capacitor are determined by the mechanical properties of the individual layers used in the capacitor and thus by the entire layer structure. The speed of sound in the individual layers, their thickness and also the impedance jumps at the boundary surfaces between the layers contribute to the resonant behavior. A high-impedance difference between two adjacent layers implies a high reflection at the boundary surface, so that a standing wave can form between two boundary surfaces with impedance jumps, which turns the component into a resonator.
In a layer structure however, there are normally a number of material transitions and thus potential reflective boundary surfaces that lead to the appearance of several resonances. A capacitor therefore has a multilayer structure that comprises at least one lower and one upper electrode as well as a dielectric arranged between them, wherein resonant oscillation modes of bulk acoustic waves can propagate in the layer structure. In this layer structure, a resonant behavior is adjusted by suitable selection of materials, the number of layers used and their thicknesses such that the resonant frequencies of the oscillation modes capable of propagation lie outside three essential band ranges employed and used in mobile telephones. In particular this is a first band range between 810 and 1000 MHz, a second band range between 1700 and 2205 MHz and a third band range between 2400 and 2483.5 MHz. The first and second band range are used for the two GSM mobile telephone bands as well as for UMTS, while the third frequency range is used for WLAN. In a capacitor, therefore, resonators are deliberately formed and their resonant frequencies are arranged in a suitable manner such that the aforementioned band ranges are sufficiently remote from them that the capacitor has a sufficiently high quality factor in the aforementioned band ranges. Between the band ranges, the quality factor of the capacitor can decline to arbitrarily low values, but it remains at a sufficiently high level in the band ranges in which it is to be used that the capacitor is completely usable in the aforementioned band ranges.
Strontium titanate, barium/strontium titanate or lead zirconate/titanate are used as a preferred dielectric in the capacitor. All of these materials have a voltage-dependent relative dielectric constant, and make the capacitor tunable.
It is advantageous for the use of the capacitor to design the layer structure such that a fourth band range between 5150 and 5250 MHz, with the WLAN frequencies situated there, remains free. The capacitor with these four band ranges free of resonant frequencies, and accordingly sufficiently high quality factors in the band ranges, is universally functional for nearly all frequencies currently used in mobile communication, and can therefore be employed in the corresponding devices and circuits.
A first general solution for a capacitor with a layer structure and resonant frequencies outside the four above-mentioned band ranges is to design the entire layer structure to be thin enough that the lowest resonant frequency appears only above the fourth band range, i.e., above 5250 MHz. For this, the entire layer thickness must be markedly less than 0.5 μm. Then, however, the relatively thin capacitor electrodes, each thinner than 200 nm, are disadvantageous. For technical reasons, however, growth and adhesion layers with low electrical conductivity are necessary for the ferroelectric materials that are used, leading to higher electrical losses for the aforementioned small overall layer thickness, which severely limit the usage possibilities of such components.
A second general approach is to situate the lowest resonant frequency between 2483.5 MHz and 5150 MHz and to shift the second resonant frequency into a range above 5250 MHz. Realizing this, however, requires layer structures with individual layer thicknesses that lie beneath the optimal layer thicknesses for low losses. Therefore functional capacitors can be constructed that are improved with respect to the first solution possibility, but are not yet suitable for all usage possibilities.
A third general solution possibility lies in a capacitor with a lowest resonant frequency between 2250 and 2400 MHz, while additional resonant frequencies lie between 2483.5 MHz and 5150 MHz and/or above 5250 MHz. This requires a bandwidth of 150 MHz for the first resonant frequency. This implies that at a distance of 75 MHz away from this resonant frequency with minimal quality factor, the quality factor of the capacitor must again have risen sufficiently high. This can be achieved however, by improving the reflection at the crucial boundary surfaces. This can be achieved by constructing the boundary surface of the layer structure towards the substrate to be particularly smooth.
However, a capacitor in which an acoustic mirror is constructed in the lowest layer area is further improved. An acoustic mirror is known from the BAW (bulk acoustic wave) resonators and FBAR (film bulk acoustic wave resonator) resonators used in filter technology. It consists of at least one layer pair comprising a respective high-impedance layer and a low-impedance layer, wherein a sufficient reflection effect for the acoustic mirror appears whenever the ratio of the two acoustic impedances Z N /Z H <0.66 or the ratio Z H /Z N >1.5. In particular, heavy metals such as platinum, molybdenum, tungsten, copper, gold or TiW, whose acoustic impedances lie in the range between 40 and 100×10 6 kg/m 2 s, can be used as high-impedance layers. In particular, silicon oxide, silicon nitride or aluminum, alongside other relatively low specific-gravity materials whose acoustic impedances lie between 13 and 21, can be considered for low-impedance layers.
An acoustic mirror can be adjusted in its reflection behavior to a certain center frequency with wavelength λ m if the thicknesses for the layer pair of the mirror are adjusted to a value of λ m /4. For a wavelength λ m maximum reflection occurs with a reflection factor of 1. The bandwidth of the mirror, i.e., the frequency range in which a sufficient reflection takes place increases with decreasing quality factor of the mirror. A sufficiently high reflection effect can therefore be achieved in a mirror if several layer pairs of high and low-impedance layers are arranged one above the other and their center frequencies are offset with respect to one another. Alternatively, the quality factor of a mirror can be reduced. In a capacitor with an integrated acoustic mirror, however, the resonance of the resonators contained in the capacitor layer structure is improved in all cases, and thus their bandwidth is reduced. A layer pair well-suited for the acoustic mirror of capacitors comprises, for instance, a double layer of 800 nm platinum and 900 nm silicon dioxide. Between 0.9 and 2.1 GHz, i.e., in the range between the first and second blocking region, this layer pair has a reflectivity factor of nearly 1 relative to longitudinal waves.
A fourth possibility in principle for realizing a desired capacitor consists in the construction of a layer region with resonators and partial resonators, the lowest resonant frequency of which lies between 1000 MHz and 1700 MHz, as well as possible additional resonant frequencies between 2250 MHz and 2400 MHz as well as between 2483.5 and 5150 MHz, as well as over 5250 MHz. For this variant, sufficiently thick metallizations can be used, which result in a low electrical resistance. Moreover, a sufficient bandwidth of 700 MHz exists between the first and the second band range that the quality factor of the capacitor in the adjacent first and second band range can again increase to a sufficiently high value.
A fifth possibility in principle for realizing a capacitor lies in a layer structure having a lowest resonant frequency below 810 MHz and additional resonant frequencies between 1000 and 1700 MHz, between 2205 and 2400 MHz, between 2483.5 and 5150 MHz as well as over 5250 MHz. With a lowest resonant frequency below 810 MHz, thick electrodes with a low electrical resistance can be employed. Higher harmonic and additional resonances have a relatively narrow frequency separation between one another, however, so that an expensive and carefully adjusted layer structure is necessary to keep the desired bandwidths free of resonant frequencies
The resonators are constructed on ceramic or crystalline substrates, in particular, on crystalline silicon or on aluminum oxide. Particularly in the latter case, a dielectric layer that has a good planarization effect and compensates for the technically induced high roughness of the aluminum oxide surface is preferred as the lowest layer of the layer structure. Well suited for this are, for instance, silicon oxide and silicon nitride layers. Above this dielectric layer, the thickness of which contributes to the determination of the capacitor's resonant frequencies, it is possible to arrange additional dialectic layers. Preferably, however, the first electrode of the capacitor is arranged directly above the lowermost dielectric layer. The electrode can be single-layer or multilayer. It is possible, for instance, to provide a two-layer electrode consisting of a first highly conductive metal with low-impedance and a second electrode layer of a metal with relatively high acoustic impedance. A platinum layer, which can simultaneously serve as a growth and adhesion layer for the ferroelectric, is preferred for the high-impedance layer.
It is also possible to select the material for a multilayer capacitor electrode in such a manner that only a low impedance jump, which does not lead to any interfering reflections, appears between the two material layers. Such a layer combination is then seen by the acoustic wave as a uniform layer, and is considered as only a single layer in the calculation of the resonant frequencies.
The ferroelectric layer, which may require an adhesion layer between it and the electrode layer, preferably has a layer thickness greater than or equal to 100 nm. Due to possibly differing speeds of the acoustic wave, the optimal layer thickness for ferroelectric layers of different composition may possibly deviate from this value. An additional adhesion layer above the ferroelectric layer for improving the upper electrode layer may also be necessary. Thin layers of platinum or TiW, for example, are suited for this purpose. Because of their poor electrical conductivity, these layers are preferably designed to have a minimal thickness. The additional layers for the upper electrode then comprise at least one additional highly conductive, or merely sufficiently thick, layer of aluminum, copper, or gold, for example. Finally, one or more dielectric layers that serve as a passivation layer for the electrode layers can be provided. In addition to oxide or general ceramic layers, the passivation layer can also be an organic polymer such as BCB (benzocyclobutene), SOG (spin on glass), parylene, photoresist and other materials.
In a layer structure for the capacitor it can be necessary to introduce additional impedance jumps by means of additional layers of suitable impedance. When adjusting suitable resonances, however, it also possible to arrange layer transitions between individual layers to be invisible and thus nonreflective, to absorb the acoustic wave or to “smear” the reflection, or make it indistinct. Layer boundaries invisible to the acoustic wave are obtained between materials of identical or similar acoustic impedance. Thus, for example, silicon oxide and aluminum have nearly identical acoustic impedances, so that a silicon oxide/aluminum double layer can be considered a single layer in acoustic terms.
Viscous layers generally lead to a reduction of reflection and thus reduce the resonance of the standing wave, which improves the quality factor of the entire capacitor independently of the wavelength. In particular, the aforementioned passivation layers can be constructed as viscous layers, for example, polymer layers.
A “smeared” reflection is obtained with a phase boundary of sufficiently high roughness. Even a surface roughness with structure sizes greater than 100 nm at the boundary with the next layer leads to a reduction of the reflection. A surface roughness having structures at least 0.5 μm in size is quite suitable. A rough surface reduces the resonance, since the acoustic wave sees layers of thicknesses that differ as a function of the structure sizes at the surface, which leads to a widening of the bandwidth of the reflection and thereby reduces the intensity of the resonance.
The surface of a ceramic substrate consisting of aluminum oxide is an inherently rough surface with reduced reflection. In order not to disrupt the remainder of the layer structure with regard to homogeneity and planarity of the layers, the subsequent phase boundary can be made sufficiently flat with a first dielectric layer that has a planarizing effect. Alternatively or additionally, it is also advisable to roughen the surface of the uppermost layer and thus to realize the phase boundary with air, which boundary has a particularly high impedance jump, with lower reflexivity, or with a smeared reflection behavior.
Apart from the optimization of the layer structure, the general electrical losses of the capacitor can be reduced, and thus its quality factor generally improved. Thus the electrical resistance of the supply electrodes for the capacitor can be reduced, for example, and the electrical quality factor of the capacitor thereby increased. For this purpose, the conductivity of the supply electrodes, usually manufactured from the same material or the same layer combination as the capacitor electrodes due to the integrated manufacturing process, can be improved considerably by thickening with sufficiently conductive metals. It is possible, for instance, to provide the supply electrodes by means of a thickening of aluminum, gold, copper or other metals.
A supply line with low resistance is also achieved if a capacitor with a rectangular footprint is used and the supply line is on the edge of the longer side.
A capacitor already achieves a capacitance of 10 pF, sufficient for most circuitry environments, with a surface area of 10×10 μm2. The small component size alone makes it disadvantageous to manufacture a capacitor as a discrete component. Rather, capacitors according to the invention are integrated together with a circuitry environment on the surface of the substrate, and insofar as the latter is a semiconductor substrate, are also produced inside the substrate. It is also possible to use a multilayer substrate having several metallization planes, which are separated from one another by dielectric layers. In that way, passive components such as resistors, inductors and capacitors can be realized inside the substrate by structuring the metallization planes and connecting different metallization planes by means of plated through-holes through the dielectric layers. The capacitors can be replaced in whole or in part by the invented capacitors with ferroelectric dielectrics. It is also possible, however, to connect the aforementioned capacitors to discrete circuit elements, or to chip components comprising integrated circuits, in a circuitry environment on the substrate. A component can also comprise more than one capacitor of the invention, wherein the different capacitors can be designed for different frequency ranges, each capacitor having a maximum quality factor in a given band range, with the ranges of maximum quality factor differing for the two capacitors.
Various embodiments will be described in detail below on the basis of embodiments and the associated figures. In a schematic representation not true to scale, they show, in their entirety or in certain sections, capacitors, layer structures, circuits, and measurement curves determined on corresponding components.
DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a capacitor in schematic cross section;
FIG. 2 shows the layer structure of a capacitor in cross section;
FIGS. 3 a and 3 h show capacitors with thickened supply lines;
FIGS. 4 a and 4 b show capacitors with acoustic mirrors;
FIG. 5 shows the frequency-dependent loss angle curve of a capacitor with and without mirror layers;
FIGS. 6 a and 6 b show stacked capacitors in schematic cross section;
FIG. 7 shows the loss angle curve for the capacitor shown in FIG. 6 ;
FIGS. 8-12 show the quality factor curve of resonators with different layer structures.
DETAILED DESCRIPTION
FIG. 1 shows in schematic cross section a plate capacitor constructed as a multilayer structure on a substrate S. The substrate is suitable as a carrier substrate, preferably crystalline or ceramic in structure, and consists, for example, of glass, aluminum oxide or silicon. The capacitor comprises at least one lower electrode E 1 that is placed directly, or with the interposition of one or more electrically conductive or dielectric layers, on substrate S. A ferroelectric such as barium/strontium titanate is arranged above it as dielectric D. This dielectric can be produced with a thickness of from less than 100 nm to several 100 nm, e.g., 400 nm. Thus it is assured that only low control voltages are necessary to exploit the inherently high tunable dielectric constant fully over its entire range of variation. Even in this simple configuration, high capacitance densities of ca. 100 fF/μm2 can be achieved.
The second electrode layer E 2 is arranged above dielectric layer D. If appropriate, an additional adhesion layer can be arranged, preferably likewise electrically conductive metals or alloys, which thereby contribute to the electrode function and hence represent component layers of second, upper electrode E 2 .
FIG. 2 shows in schematic cross section an example of a layer structure for the capacitor. An electrically insulating dielectric layer DS 1 with a planarizing effect, an SiO2 layer on an aluminum oxide substrate, for example, is arranged on top of substrate S. Lower electrode layer E 1 comprises a first highly conductive metal layer ME 1 and a relatively thin combined growth and adhesion layer HE 1 . Al is preferred as conductive lower electrode layer ME 1 and platinum as adhesion layer HE 1 . Alternatively, the lower electrode is constructed as an adhesion layer sufficiently thick for conductivity, i.e., made of an electrode material with good adhesion properties for the dielectric. Dielectric layer D is a ferroelectric that is chosen with respect to its composition such that is tunable in its permittivity via voltage-applied to the electrodes. Second electrode layer E 2 arranged thereabove is again composed of an adhesion layer HE 2 and a highly conductive or sufficiently thick metal layer ME 2 . Adhesion layer HE 2 can also be multi-layer and comprise one or more layers selected from platinum, Pt—TiW, Ti, NiCr and so forth. The necessity of such an adhesion layer is dependent on the exact layer structure in question and on the application process that was selected. Adhesion layers HE 1 and HE 2 are optimized to the minimal layer thickness in order to not reduce the conductivity of the overall electrode layer E 1 or E 2 unnecessarily.
Upper highly conductive metal layer ME 2 is preferably a highly conductive metal such as aluminum, gold, copper, or other appropriate metals. The upper electrode can alternatively consist of a single layer, e.g., a thick platinum layer.
Finally, a passivation layer, selected from silicon nitride, silicon oxide or the polymers and glasses mentioned above, is applied.
In the general layer structure shown, there are acoustically relevant boundary surfaces due to sufficiently high impedance differences between the substrate and dielectric layer DS 1 , between lower conductive layer ME 1 and lower adhesion layer HE 1 , between upper adhesion layer HE 2 and upper conductive layer ME 2 , between upper conductive layer ME 2 and passivation layer PS, as well as between the passivation layer and the surrounding medium, which is usually air.
In the illustrated example, a total of four component resonators are formed, each associated with its own resonant frequency f 1 -f 4 . The dimensions of the component resonators are labeled in the figure by the corresponding double arrows. Due to the selected layer thickness ratios, f 1 >f 2 >>f 3 >f 4 . In general, the resonant frequency is higher the thinner the layer stack is in which the resonance develops. The layer stacks are preferably as thin as possible.
An overall thickness of less than 500 nm may result for the layer stack between the lower conductive layer and the upper conductive layer, which is associated with resonant frequency f 1 , wherein an acoustic resonant frequency of more than four gigahertz can be associated with such a stack.
Resonance f 2 forms between lower conductive layer ME 1 and the passivation layer. For a minimum layer thickness of the upper metallization of ca. 100 nm to ca. 1 μm, a resonant frequency f 2 of less than one gigahertz to ca. four gigahertz can be associated with this stack.
As a function of the thickness of lower dielectric layer DS 1 or passivation layer PS, the additional resonant frequencies f 3 and f 4 are arranged at correspondingly lower frequencies. However, the layer structure is always optimized such that the capacitor has no resonance in the above-mentioned three band ranges. In the layer structure represented in FIG. 2 , the resonant frequency f 4 can be suppressed or reduced by a roughening of the surface of the passivation layer, or by use of appropriately viscous or polymeric materials, so that a higher quality factor can be maintained in the band range corresponding to resonance f 4 , despite resonance occurring to some extent.
FIGS. 3 a and 3 b show two possibilities for increasing the quality factor of a capacitor independently of the layer structure in the area of the active capacitor in a layer structure shown for the sake of example in FIG. 2 . FIG. 3 a shows a cross section of a capacitor in which electrode layers E 1 and E 2 are elongated to form electrical supply lines. Outside of the area in which the two electrodes E 1 and E 2 overlap each other, the electrode layers or the supply lines formed from them are thickened with a highly conductive material so that their series electrical resistance is reduced. FIG. 3 b shows a schematic plan view of a capacitor in which, additionally or alternatively to the thickening, the footprint of the capacitor is designed such that the supply line is arranged above the longer side edge of the rectangular footprint of the capacitor.
FIGS. 4 a and 4 b show, on the basis of a schematic cross section, an additional configuration of a layer structure usable for a capacitor. Additionally or alternatively to the layer structure according to FIG. 2 , this capacitor has an acoustic mirror, which features at least one pair of mirror layers comprising a low-impedance layer and a high-impedance layer, underneath lower electrode E 1 . FIG. 4 a shows a capacitor with a pair of mirror layers, and FIG. 4 b shows a connector with a second pair of mirror layers. The mirror layers are formed, for instance, of a layer combination of 800 nm platinum and 900 nm silicon oxide, which achieve a high reflectivity factor of nearly 1 in the range from 0.9 GHz to roughly 2.1 GHz. The width of the acoustic resonance is markedly reduced with the aid of such mirror layers, so that the frequency-related useful range outside the resonances increases.
FIG. 5 shows the curve of the loss angle tan δ versus frequency f. The different measurement curves correspond to a layer structures without a mirror layer, with one pair of mirror layers and with two pairs of mirror layers, and are presented one above the other for comparison. The first and second blocking regions are entered as thick bars. It is seen that the width of the resonance is sharply reduced already with one pair of mirror layers, and can be further reduced with a second pair of mirror layers. The bandwidth of the resonance can be adjusted to less than 100 MHz. The illustrated loss angle curves are provided for layer structures in which, in addition to the aforementioned mirror layer pair, the two electrodes E 1 and E 2 are each constructed of 600 nm Pt, and a roughly 30 μm-thick first dielectric layer of SiO 2 is arranged directly above aluminum oxide substrate S. The resonant frequency of this layer structure is roughly 1405 MHz; the width of the resonance (without mirror layers) is more than 200 MHz. With one pair of mirror layers, the width is reduced to 50 MHZ, and with two it is reduced to 30 MHz.
FIGS. 6 a and 6 b show in schematic cross section an additional variant of a layer structure usable for the capacitor. Above second electrode E 2 , a second ferroelectric dielectric D 2 is arranged; above the latter, a third electrode E 3 , a third dielectric layer D 3 and fourth electrode E 4 are arranged. This results in a stack of three component capacitors, which can be connected in parallel, for example. FIGS. 6 a and 6 b show such a structure with the interposition of an acoustic mirror between substrate and first electrode E 1 , which is constructed here of two pairs of mirror layers. The thickness of the mirror layers and the selection of their material also corresponds in the stack capacitor to that of the single capacitor, but can deviate therefrom.
FIG. 7 shows the curve of the loss angle versus frequency for the illustrated stack capacitor in comparison to a stack capacitor without acoustic mirror. Due to the increased number of layers in the layer structure, there is also an increase in the number of possible resonances, which are distinguished by a large loss angle and thereby a low quality factor of the capacitor in the respective frequency range. A first and a second hand range that according to the invention are to be free of resonances, together with the required suppression levels, are drawn in the figure in the form of horizontal bars. It is shown that the curve in solid lines, which is associated with the stack capacitor without an acoustic mirror, in part extends, due to the broadened resonances, into the band range envisioned for use of the capacitor. On the other hand, the curves that are associated with a stack capacitor with one pair of mirror layers (dashed line), or with two pairs of mirror layers as in FIGS. 6 a and 6 b (dotted line), show substantially more narrow resonances directly above 1100 MHz and at around 1600 MHz, which are arranged such that the capacitor has only a slight loss angle tan δ in the first and second blocking regions and therefore a high quality factor. This implies that even for an elaborate layer structure with a number of individual capacitor layers, a capacitor of the invention with resonances outside the blocked band ranges can be obtained by appropriate optimization.
Table 1 below again provides the layer structures of the embodiments described on the basis of FIGS. 4-7 .
TABLE 1
Layer/Example
1/FIG. 4a
2/FIG. 4b
3/FIG. 6
E4
—
—
600
nm Pt
D3
—
—
200
nm BST
E3
—
—
600
nm Pt
D2
—
—
200
nm BST
E2
600
nm Pt
600
nm Pt
600
nm Pt
D
200
nm BST
200
nm BST
200
nm BST
E1
600
nm Pt
600
nm Pt
600
nm Pt
NI
—
900
nm SiO 2
900
nm SiO 2
HI
—
800
nm Pt
800
nm Pt
NI
900
nm SiO 2
900
nm SiO 2
900
nm SiO 2
HI
800
nm Pt
800
nm Pt
800
nm Pt
DS
30
μm SiO 2
30
μm SiO 2
30
μm SiO 2
S
Al 2 O 3
Al 2 O 3
Al 2 O 3
Additional concrete layer structures will be specified below and investigated with respect to their suitability in regard to high quality factor in the blocked band ranges. For this purpose, the structure will be kept constant from the substrate to the ferroelectric dielectric in most examples, and only upper electrode E 2 will be varied.
In a first group, a layer structure over a substrate S of aluminum oxide, there are a first dielectric layer DS 1 of 50 μm silicon oxide and 30 nm titanium oxide, a first electrode E 1 with a conductive layer ME 1 of 500 nm platinum and a first adhesion layer HE 1 of 50 nm platinum, as well as a dielectric layer D of 120 nm barium/strontium titanate. Second electrode E 2 follows, and above that, 300 nm Si 3 N 4 as passivation. Second electrode E 2 is then varied as follows:
TABLE 2
No.
Second Electrode E2
First Resonance
4
960 nm Al
1.5
GHz
5
725 nm Pt
1.5
GHz
6
100 nm Pt - 80 nm TiW - 200 nm Al
3
GHz
7
50 nm Pt - 50 nm TiW - 200 nm Al
3
GHz
8
100 nm Pt - 80 nm TiW - 690 nm Al
1.5
GHz
9
100 nm Pt - 80 nm TiW - 115 nm Cu
3
GHz
10
100 nm Pt - 80 nm TiW - 840 nm Cu
1.5
GHz
11
100 nm Pt - 80 nm TiW - 100 nm Au
3.5
GHz
12
100 nm Pt - 80 nm TiW - 560 nm Au
1.5
GHz
Example 13 has the following layer sequence over a substrate S of aluminum oxide: 50 μm silicon oxide-1600 nm Pt-120 nm BST-440 nm Pt-1800 nm W-2500 nm Al.
The resonances lie outside of the useful band ranges due to the use of a thicker Pt lower electrode and an upper multilayer electrode. The electrical losses are reduced with respect to the other examples by the thicker electrodes.
FIG. 8 shows the curve of quality factor Q versus frequency for relatively thin electrodes, as in examples 6, 9 and 11. In the variant with gold (solid line) or copper (thick dashed line) as conductive upper metal layer ME 2 , the resonance with low electrical quality factor lies at about 4 GHz. One thereby obtains acceptable electrical quality factors of more than 60 both in the two gigahertz range (second band range) and in the five gigahertz range (fourth band range). Since aluminum (see thin dotted line) has an acoustic impedance comparable to silicon, the boundary surface between the two layers has no acoustic effect, so that the boundary surface of silicon nitride and air is responsible for the first resonance. It therefore lies at a lower frequency of ca. three gigahertz. For this embodiment with 200 nm aluminum as upper conductive metal ME 2 , this results in a lower quality factor at five gigahertz.
FIG. 9 shows the quality factor curves for three additional embodiments based on a structure similar to FIG. 8 . Only the layer thickness of the conductive material used for second electrode E 2 is increased. The three illustrated curves correspond to embodiments with 590 nm Al (example 14), 400 nm Au (example 15) and 600 nm Cu (example 16). The other layer materials and layer thicknesses remain unchanged from the embodiments associated with FIG. 8 . With the higher thicknesses of the aluminum, copper or gold electrode, it is attempted to shift the first resonance into the range between 1 GHz and 1.7 GHz, and to achieve as high an electrical quality factor as possible in all relevant frequency ranges, i.e. the first to the fourth band ranges. This is not possible in this case with gold and copper. With aluminum as the upper conductive layer, the quality factor becomes low only in the lower range of the 2 GHz band, since the latter lies in the vicinity of the resonance at roughly 1.7 GHz. The quality factor for the first band range is high for all three embodiments, and the quality factor for the third and fourth band ranges remains sufficiently high for all three embodiments.
FIG. 10 shows the quality factor curves for three additional embodiments, in which the same layer structure and the same line association is used as in FIGS. 8 and 9 , and the upper conductive layer is merely further increased in thickness. Three embodiments are considered, in which the upper conductive layer consists of 560 nm of aluminum (example 8), 690 nm of gold (example 12) or 840 nm of copper (example 10). In this embodiment, the requirement for a high electrical quality factor at 5 GHz and 2.5 GHz, i.e. in the third and fourth band range, is dropped. In return, a high quality factor can be achieved in the 2 GHz range with all three embodiments due to the increased layer thicknesses.
FIG. 11 shows the quality factor curves for two additional embodiments which again have a layer structure corresponding to FIGS. 8-10 , but wherein upper conductive layer ME 2 was further increased. Two embodiments with 960 nm Al (example 4, see dashed line) and 725 nm Pt (example 5, see solid line), respectively, were studied. For the embodiment with aluminum, it was shown that the boundary surface with the air and the boundary surface of the lower platinum layer with aluminum were the most acoustically active. Therefore a high electrical quality factor can be obtained with aluminum in all relevant frequency ranges, i.e., in the first through fourth band ranges. This cannot be achieved with only platinum as the conductive layer of the upper electrode.
FIG. 12 shows the electrical quality factor curve of a capacitor according to example 17, in which a thick, 1800 nm platinum layer is used. The remainder of the layer structure corresponds to examples 4-11. A good quality factor at 1 GHz and 2 GHz as well as a medium quality factor at 2.5 and 5 GHz are observed.
Above an aluminum oxide substrate, the layer structure of example 13 has 50 μm of silicon oxide as a dielectric layer DS, 1600 nm of platinum as first electrode E 1 , 120 nm of BST as dielectric D, and as an upper electrode E 2 a triple layer consisting of 440 nm of platinum, 1800 nm of tungsten and 2500 nm of aluminum.
Due to the overall very thick electrodes, the electrical resistance is markedly reduced, so that high quality factors are achieved outside the acoustic resonances. However, many resonances occur because of the relatively thick overall structure, but with the specified layer structure they all lie outside the usable band ranges one through four. The highest quality factors up to this point are achieved in all band ranges with these embodiments.
An additional further optimized embodiment 18 has, above an aluminum oxide substrate, a structure that comprises the following layers: 50 μm of silicon oxide, 30 nm of titanium oxide, 525 nm platinum, 200 nm of BST, 700 nm of Pt and 350 nm of PSG as a passivation layer PS. High quality factors are achieved in all four band ranges with this embodiment as well. The resonant frequencies that can form in the layer structure all lie clearly outside the band ranges.
It is shown that with the layer structure, it is possible to realize capacitors that have high quality factors in all four band ranges used for mobile communication, and are therefore suitable for use in circuitry and circuits that operate with one or more of these frequencies. The capacitors are therefore suitable for use in matching circuits, amplifier circuits, filters and other circuits inside terminal devices for mobile communication, and in particular for use in cell phones. Circuits with these capacitors can be produced in integrated form on suitable substrates and connected to one another. For integrated interconnection, structuring steps are necessary that take place after deposition of the first or second and possibly additional electrode layers, as well as after deposition of the dielectric or ferroelectric. The capacitors are tunable with respect to their dielectric constant, and therefore their capacitance, by an application of a bias voltage. It is therefore possible to construct variable circuits that can be matched to an external environment by virtue of the tunability of their capacitance. In particular, the capacitors can be set up for different operating frequencies and optimized to the respective operating frequency by appropriate tuning. In this way it is also possible with a single circuit to realize different constellations, each of which can be matched to a given usable band range. It is therefore also possible to markedly reduce the complexity of the circuitry environment of multi-band or multi-mode terminal devices with the tunable capacitors, since what hitherto were separate circuits can now be realized with a single tunable circuit. In addition to the complexity, the space requirements for the circuits as well as the costs of the circuit are reduced.
It was only shown in the embodiments that suitable layer structures can be realized, but suitable realizations are not limited to the embodiment examples that were shown. It therefore lies within the scope to modify the layer structures by omission of individual layers, addition of layers, by changes of material or by changes of thickness.
The quality factor of the capacitors in all embodiments shown can be further improved by using acoustic mirrors, whereby the widths of the resonances appearing in the layer structure can be markedly reduced even with a single pair of mirror layers, consisting of a low-impedance layer NI and a high-impedance layer HI introduced in the layer structure underneath lower electrode E 1 . Conversely, the quality factor is markedly increased in the ranges outside the resonances. With acoustic mirrors, improved properties that justify the increased expense for manufacturing of the acoustic mirror can be obtained for complex optimization problems in all four band ranges. With the aid of the acoustic mirrors it is also possible to produce more complex layer structures with a plurality of individual capacitors produced one above the other that each comprise a ferroelectric layer embedded between two electrodes, and to obtain a sufficient quality factor in three or four band ranges.
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A capacitor includes a multi layer structure on a ceramic or crystalline substrate. The multilayer structure includes a lower electrode, an upper electrode, and a dielectric that is tunable by a voltage applied to the electrodes. The multilayer structure is configured such that resonant oscillation modes of bulk acoustic waves can be propagated in the multilayer structure and such that the resonant frequencies of the oscillation modes are outside a first band range of between 810 and 1000 MHz, second band range of between 1700 and 2205 MHz and third band range of between 2400 and 2483.5 MHz.
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This is a continuation of co-pending application Ser. No. 22,286 filed on 3/5/87, now abandoned.
BACKGROUND OF INVENTION
The field of art to which this invention pertains is homopolymers and copolymers of vinylphenol.
Homopolymers and copolymers of 4-hydroxystyrene, or p-vinylphenol as it is also called, are known compositions which have many uses, such as in the manufacture of metal treatment compositions and photoresists. Polymers of p-vinylphenol can be made by polymerizing p-vinylphenol itself. However, p-vinylphenol is an unstable compound and must be refrigerated to prevent it from polymerizing spontaneously. Even under refrigeration, the monomer will slowly polymerize to low molecular weight polymers. 4-Acetoxystyrene, the acetic acid ester of p-vinylphenol, is a stable monomer which can be readily homopolymerized and copolymerized to low, medium and high molecular weight polymers. After polymerization, the phenolic ester group can be hydrolyzed to produce p-vinylphenol polymers.
Corson et. al., Journal of Organic Chemistry, 23, 544-549 (1958), describe a 5 step process for making p-vinylphenol from phenol. The phenol is first acetylated to p-hydroxyacetophenone which is then acetylated to p-acetoxyacetophenone. This compound is hydrogenated to p-acetoxyphenylmethyl carbinol which is then dehydrated to p-acetoxystyrene. The p-acetoxystyrene is saponified to p-vinylphenol using potassium hydroxide. Packham, in the Journal of the Chemical Society, 1964, 2617-2624, describes the hydrolysis of crosslinked poly-4-hydroxystyrene by refluxing the polymer in alkaline aqueous dioxane for 2 days. In U.S. Pat. No. 4,544,704, a copolymer of styrene and p-isopropenylphenylacetate is hydrolyzed with aqueous sodium hydroxide in methanol and toluene using a small amount of benzyltrimethylammonium chloride as a phase transfer agent. Arshady et. al., Journal of Polymer Science, 12, 2017-2025 (1974), hydrolyzed copolymers of styrene and acetoxystyrene to the vinylphenol polymer using hydrazine hydrate in dioxane.
The ester interchange reaction of poly (4-acetoxystyrene) in methanol using sodium methylate is described in U.S. Pat. No. 2,276,138. It is also stated in the patent that resinous polymers are obtained by the treatment of monomeric 4-acetoxystyrene with potassium hydroxide in methanol both cold and hot and with methanol using sulfuric acid as the ester interchange catalyst.
The hydrolysis or methanolysis of polymers of 4-acetoxystyrene is very difficult to carry to 90 percent or above completion. Also, it is extremely difficult to remove all traces of alkali metal salts which can be detrimental for some applications and uses of the vinylphenol polymer.
SUMMARY OF INVENTION
This invention pertains to a process for hydrolyzing polymers of 4-acetoxystyrene to polymers of 4-vinylphenol. More specifically, the invention relates to an alcoholysis process using acids as the alcoholysis catalyst.
By the process of this invention, polymers of 4-acetoxystyrene are slurried in an alcohol and are hydrolyzed to polymers of 4-vinylphenol by heating at about 30° C. to about 65° C. in the presence of an acid for a time sufficient to hydrolyze the acetoxy group to phenolic groups as indicated by dissolution of the polymer in the alcohol. The 4-vinylphenol polymer is recovered as an alcohol solution or can be recovered neat.
DETAILED DESCRIPTION OF INVENTION
Polymers useful in this invention are homo and copolymers of 4-acetoxystyrene. 4-Acetoxystyrene can be polymerized in solution, suspension, emulsion, or bulk using well known free radical catalysts, such as, for example, the peroxide and the azo compounds. 4-Acetoxystyrene will homopolymerize readily in the same manner that styrene homopolymerizes and can also be copolymerized with styrene and with monomers which are copolymerizable with styrene. Examples of comonomers, in addition to styrene, are vinyl toluene, chlorostyrene, bromostyrene, alpha-methyl styrene, the diene monomers, such as butadiene, the acrylate and methacrylate ester monomers, such as methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate and 2-ethylhexyl acrylate. The preferred comonomer is styrene.
Useful copolymers contain about 1 to about 99 parts of 4-acetoxystyrene to about 1 to about 99 parts of monomer copolymerizable therewith. Preferred copolymers contain about 25 to about 75 parts of 4-acetoxystyrene to about 75 to about 25 parts of monomer copolymerizable therewith.
Acids useful in this invention are mineral acids and organic acids as well as Lewis acids which have dissociation constants in aqueous solutions, i.e., pK a , of less than 2 and, preferably, less than 1. Examples of such acids include hydrochloric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluene sulfonic acid, benzyl sulfonic acid, dichloroacetic acid, trichloroacetic acid, iodic acid, boron trifluride, aluminum chloride, stannic chloride and the like. The preferred acids are hydrochloric acid, sulfuric acid, methanesulfonic acid and p-toluene sulfonic acid. The amounts of acid used in the process of this invention can vary over a wide range from about 1 percent by weight based on the weight of 4-acetoxystyrene polymer up to about 40 percent by weight. Preferably about 1 to about 10 weight percent of acid is used.
Alcohols useful in this invention are one to four carbon alcohols i.e., methanol, ethanol, the propanols and the butanols. The preferred alcohols are methanol and ethanol with methanol being most preferred.
In carrying out the process of this invention, the 4-acetoxystyrene polymer is slurried in an alcohol in the amount of about 5 percent by weight of polymer up to about 40 percent by weight of polymer in the alcohol wherein the percentages are based on the total weight of polymer and alcohol. The slurry is stirred and the acid catalyst is added. The reactants are held at a temperature of about 20° C. to about 65° C. until the polymer dissolves in the methanol indicating complete conversion of the acetoxy groups to phenolic groups. Generally, this heating period will vary from about 1 hour to about 20 hours. When solution is obtained, indicating the completion of the alcoholysis reaction, the reactants are then neutralized with base to a pH of about 5 to about 7. Under basic conditions, the phenolic groups readily undergo oxidation to quinoid structures and, consequently, undesirable color formation. The solution is then filtered to remove precipitated salts. The solution of the 4-vinylphenol polymer in the alcohol can be used as is. The polymer can also be recovered as a solid by distilling off the volatile solvents and can be purified by being redissolved in a solvent, such as acetone, followed by coagulation in water. The recovered polymer is dried and ground into a fine powder. In an alternative process, the hydrolyzed alcoholic solution can be coagulated in water without neutralization and can be recovered as a solid.
The following examples describe the invention in more detail. Parts and percentages are by weight unless otherwise designated.
EXAMPLE 1
To suitable reactor are added with stirring 5 parts of poly(4-acetoxystyrene), 50 parts by volume of methanol and 1 part by volume of sulfuric acid. The reactor contents are heated to 40° C. and are held at this temperature for 1 hour. At the end of the heating period, the dispersed polymer is completely dissolved in the methanol. Sodium hydroxide pellets, approximately 1 part, are added to make the solution weakly acidic (pH 5-7). The reactor contents are cooled overnight in a refrigerator and are then filtered. The methanol and methyl acetate which are formed in the reaction are then removed in a rotating evaporator. The resulting polymer is dissolved in 50 parts by volume of acetone and the solution is dropped into 1,600 parts of water. The solids are removed from the water by filtration and are dried. The resulting polymer in 80 percent yield is completely hydrolyzed poly (4-vinylphenol) as indicated by infrared analysis. The glass transition temperature of the polymer is 183° C., with a thermal decomposition on set at 360° C.
EXAMPLE 2
To a suitable reactor are added 2 parts of poly-(4-acetoxystyrene), 50 parts by volume of methanol and 0.5 part by volume of concentrated hydrochloric acid. Agitation is begun and the reactor contents are heated to 50° C. After 1.75 hours heating, the polymer is completely dissolved in the methanol. The solution is filtered and 0.5 part of sodium hydroxide is added, followed by filtration. The solvents are removed in a rotatory evaporator and are then dissolved in 20 parts by volume of acetone. The solution is then slowly added to 300 parts of water containing 1 part by volume of concentrated hydrochloric acid. The polymer is removed by filtration and is dried. The resulting polymer in 86 percent yield is identified as poly (4-vinylphenol) by infrared analysis. The glass transition temperature of the polymer is determined to be 169° C. by Differential Scanning Calorimeter (DSC).
EXAMPLE 3
Using the same procedure described in Examples 1 and 2, 2 parts of poly (4-acetoxystyrene), 50 parts by volume of methanol and 0.5 part of methanesulfonic acid are reacted at 50° C. for 30 minutes. At the end of this heating period, complete solution of the polymer is obtained. The polymer product isolated as described in Example 1 and 2 is recovered in 85 percent yield and is identified as poly (4-vinylphenol) by infrared analysis.
EXAMPLE 4
Using the same procedure described in the preceding Examples, 4 parts of a 50, 50 copolymer of 4-acetoxystyrene and styrene are reacted with 50 parts by volume of methanol and 1 part by volume of concentrated hydrochloric acid. After 1 hour heating, complete hydrolysis of the acetoxy groups to phenol groups is obtained.
EXAMPLE 5
To a suitable reactor are added 50 parts of methanol, 5 parts of poly(4-acetoxystyrene) and 0.5 parts of methanesulfonic acid. The reactants are stirred at room temperature under a nitrogen atmosphere overnight (approximately 19 hours). During this time all solids are completely dissolved. The resulting solution is then dropped into 1,000 parts of water. The precipitated solids are removed from the water by filtration and are washed thoroughly with water to remove any acid impurities. The white solid thus obtained is dried in a vacuum oven at 50° C. overnight. The resulting polymer in 100 percent yield is completely hydrolyzed poly(4-vinylphenol) as indicated by infrared analysis.
EXAMPLE 6
To a suitable reactor are added 50 parts of absolute ethanol, 2 parts of poly(4-acetoxystyrene) and 0.5 part of methanesulfonic acid. The reactants are stirred overnight at room temperature under a nitrogen atmosphere (approximately 19 hours). At the end of this period, the polymer is completely dissolved in the ethanol. The resulting solution is then dropped into 1,000 parts of water. The solids are removed from the water by filtration and are washed with a large excess of water to remove any acid impurities. The resulting white polymer is dried in a vacuum oven at 50° C. overnight. The polymer is obtained in 95 percent yield and is completely hydrolyzed poly(4-vinylphenol) as indicated by infrared analysis.
EXAMPLE 7
Using the same procedure as described in the preceding examples, 2 parts of poly(4-acetoxystyrene), 2 parts of boron trifluoride etherate and 50 parts of methanol are reacted overnight at room temperature. At the end of this period, the resulting polymer solution is dropped in 1,000 parts of water, the precipitated polymer is washed with water and is then dried in a vacuum oven at 50° C. overnight. The polymer product is recovered in 100 percent yield and is completely hydrolyzed poly(4-vinylphenol) as indicated by analysis.
EXAMPLE 8
To a suitable reactor are added 55 parts of distilled water, 0.05 part of potassium persulfate and 0.5 part of sodium lauryl sulfate. When solution is obtained, 22 parts of para-acetoxystyrene are added. Nitrogen is bubbled through the mixture to displace the air and to disperse the para-acetoxystyrene monomer. The mixture is then stirred for 5 hours at 75° C. The resulting polymer emulsion is then dispersed in 200 parts of methanol. Concentrated hydrochloric acid, 3 parts, is added and stirring is conducted overnight. At the end of this period, the dispersed polymer is completely dissolved in the methanol. The resulting solution is dropped into 3000 parts of water, is filtered to remove the solids and the solids are washed with a large excess of acid to remove acidic impurities. The snow white polymer is dried in a vacuum oven at 50° C. overnight to obtain 14.3 parts (75 percent yield) of completely hydrolyzed poly(4-vinylphenol) as indicated by infrared analysis.
The 4-vinylphenol polymers obtained by this invention are used to cure epoxy resins, e.g., the diglycidyl ether of Bisphenol A. The polymers are also converted into epoxy resins by reacting them with epichlorohydrin using caustic as the condensation catalyst and the dehydrohalogenation catalyst.
The principles, preferred embodiments and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrating rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
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Polymers of 4-vinylphenol are made by the acid catalyzed transesterification of polymers of 4-acetoxystyrene in an alcohol. The 4-vinylphenol polymers are useful as epoxy resins curing agents and as the phenolic base for epoxy resin per se.
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FIELD OF THE INVENTION
This invention is directed towards a biological treatment system which is suitable for removing and/or degrading a wide variety of contaminants. The treatment system is able to effectively handle volatile organic compounds (VOCs), volatile organic hazardous air pollutants (VOHAPs), light to middle weight petroleum distillates, and a variety of other organic pollutants. The treatment system is able to effectively treat these pollutants from both gas and liquid waste streams.
BACKGROUND OF THE INVENTION
The Clear Air Act Amendment (CAAA) of 1990 requires industrial and commercial facilities to control emissions of a wide range of Volatile Organic Hazardous Air Pollutants (VOHAP), Volatile Organic Compounds (VOCs), particulates, and gases causing acid rain and precursors for depletion of stratospheric ozone layers. The CAAA contains 10 titles, each addressing specific guidelines and compliance rules for each area of concern.
Title III of the CAAA requires all industrial and commercial facilities located within “non-attainment” areas to reduce their VOC emissions below the threshold value. The term “non-attainment” means areas or metropolis which have not met the National Ambient Air Quality Standards (NAAQS) in terms of ozone, NO x and particulate matter.
Title III of the CAAA requires 174 source categories/industry groups requiring control of emissions of 188 Hazardous Air Pollutants (HAPs). Each source category is a specific type of industrial or commercial operations which emits pollutants to the ambient air. A facility becomes a major source when it emits over 10 tons per year of a single HAP, or over 25 tons per year of all HAPs combined into the air.
Further, industry and regions in all parts of the country are undertaking aggressive efforts to limit the release of all types of hazardous materials. Public reporting criteria have increased the scrutiny and public pressure on all industries which generate or release toxic or hazardous materials. As a result, many industries are undertaking renewed efforts to control the production or release of hazardous materials.
Title III of the CAAA exposes numerous industrial emission sources which were not regulated or controlled before. These sources require installation of emission control technologies. At present, many industrial and commercial facilities have turned to aqueous scrubbing techniques or thermal oxidation processes such as incineration to curb their emissions. Incineration, while achieving a high destruction efficiency, is expensive in terms of capital and operating costs. Further, off-site incinerators which may serve many industries, face ever more opposition from citizens who have health concerns over incinerations efficacy and safety. Incineration of halogenated VOCs and HAPs are also extremely corrosive to the contact parts and may produce highly toxic substances such as dioxin.
Aqueous scrubbing technologies for VOC control do not have the corrosion or toxic byproduct formation problems like the incineration technologies. However, the scrubbers can only be effective for hydrophilic VOCs and HAPs and also require effective means for disposal of scrub water. For hydrophobic contaminants, such as the majority of the regulated VOCs and HAPs, aqueous scrubbing is generally not effective for emission control.
Both the incinerator and the scrubber technologies are not well suited or compatible for accepting and treating facility wastewater. In other words, both the technologies are applicable for treatment of only air streams. For hydrophilic contaminants, scrubbers could potentially use facility wastewater. However, since scrubbers merely transfer the contaminants from the gaseous to the liquid phase, and do not destroy, degrade or decompose, other forms of treatment operation(s) are necessary to dispose or discharge the scrub water.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a material and process which effectively treats a diverse group of pollutants.
It is a further object of this invention to provide a material and a process which can effectively remove pollutants from gaseous as well as liquid waste streams.
It is a further and more particular object of this invention to provide an apparatus and process which uses selected sorbents along with bio-solids to first remove (separate/concentrate) and to then degrade contaminants from a waste stream.
These and other aspects of the invention are made possible by features of applicants' AGB (Ashalata, Gostha Bihari) Process which involves the use of a novel bio-reactor utilizing microorganisms embedded in selective sorbents to sorb and bio-oxidize VOCs and HAPs from facility exhausts. As used herein, the term “sorb” includes both adsorptive and absorptive capabilities. In a single operative step, a multistage unit provides for the initial removal and subsequent degradation/detoxification of organic contaminants by utilizing bio-solids, selective sorbents, moisture and micro-nutrients.
Wastewater may be used to provide the moisture and part of the organic (carbon) food sources for the bio-reactor. The wastewater may be sprayed directly over the bio-solids and the sorbents. Depending on its characteristics, the wastewater may be pretreated or conditioned so as to be conducive to the bio-solids and the sorbents. A facilities' gaseous emissions are then passed through a multistage sorption unit of the bio-reactor. Each stage of the sorption unit is stacked with a blended mixture of selective sorbents and bio-solids. Depending on the characteristics of the contaminants, the mixture may additionally contain pH buffering ingredients, surface active agents and boosters to enhance selective metabolic activities. The sorbents and the bio-solids are kept moist by adding preconditioned wastewater in the form of fine mists or globules.
As the contaminated emissions passes through the stages of the bio-reactor, the selective sorbents capture the contaminants. Once captured, the contaminants provide a metabolic source for the microorganisms. Oxygen and micronutrients such as nitrogen (N), phosphorous (P) and potassium (K) are supplied via the wastewater and aids in the process of bioxidation or metabolization which converts the contaminants to CO 2 , H 2 O and trace quantity of mineral salts. The mineral salts are only formed for contaminants containing atoms other than carbon (C), oxygen (O) and hydrogen (H). The treated exhaust exiting the last stages essential contains air, CO 2 , H 2 O vapor, and ultra trace quantities of non-reacted contaminants.
The integrated AGB Process collects the facility wastewater and performs pretreatment or conditioning. The conditioning entails reducing the concentrations of the wastewater contaminants to a level which enhances the subsequent injection into the sorption unit of the bio-reactor. The primary unit operation for conditioning is a stripper cum bio-reactor vessel where the wastewater is pulsated in the presence of sorbents and bio-solids similar to those used in the sorption unit. The pulsation treatment allows the microbes sufficient time to bio-oxidize and reduce the wastewater contaminant concentration. The pulsation also strips (dislodges) the volatile contaminants such that it can be combined with the facility exhaust for passage through a BIO-SORPTION unit. Moreover, the pulsation also suspends and grows the microbes in an aerobic state and stimulates the growth of microbes most conducive for bioremediation of the contaminants.
One part of the wastewater, after pulsation, is generally filtered before injection into the bio-treatment unit. Following filtration, the filtered wastewater is introduced to the bio-treatment unit along with the gaseous emissions. The other part of the pretreated wastewater can either be discharged or reused within the facility.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 is a schematic view of the AGB Process.
FIG. 2 is a chart entitled “Table-2” showing the performance data for removal of VOC mixtures.
FIG. 3 is a chart entitled “Table-3” showing the performance data for removal of hazardous air pollutants.
FIG. 4 is a chart entitled “Table-4” showing the performance data for removal of light hydrocarbon mixtures.
FIG. 5 is a chart entitled “Table-5” showing the reduction in the VOC concentration.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
For a better understanding of the invention, reference may be made to the embodiments exemplary of the invention shown in accompanying FIG. 1, which is a schematic of the AGB Process.
Referring to FIG. 1, the exhausts from a production or manufacturing facility containing VOCs and HAPs are drawn by a high pressure centrifugal blower ( 2 ). The exhausts can be combined with the stripping air emanating from the stripping/bio-oxidation tank ( 1 ). Tank ( 1 ) receives facility or plant wastewater containing VOCs and HAPs. Depending on the type of contaminants, bio-solids are periodically added to tank ( 1 ) for bio-oxidation. Tank ( 1 ) is equipped with devices for injection of compressed air and/or low pressure steam to facilitate dislodging, stripping and transport of the contaminants to the suction side of blower ( 2 ). Tank ( 1 ) is also equipped with a device for temperate indication and control to facilitate effective stripping and concurrent bio-oxidation. Tank ( 1 ) is operated within a temperature range of 80° F.-150° F. The diffuser ring provides a mechanism for adding stripping fluids uniformly.
Blower ( 2 ) is powered with an electric motor to impart sufficient kinetic and pressure energies to overcome line losses and pressure drops. Blower ( 2 ) discharges the combined exhausts and the stripped air to a bio-treatment column known as the BIO-SORPTION unit ( 3 ). The BIO-SORPTION unit ( 3 ) is packed with three or more stages of mixtures of selective sorbents inert packing material and bio-solids. Each stage is maintained with a packing height of 2 ft. to 4 ft. The top of each stage is sprayed as needed with pretreated wastewater to maintain preferred moisture levels within the packed mixtures. Spraying is accomplished with several mist nozzles fed by the high pressure water pump ( 6 ). To protect the nozzles from clogging, the pretreated wastewater, before injection, is filtered using a backwash filter ( 7 ). From time-to-time, the backwater filter ( 7 ) is backwashed to remove solids which are returned to the tank ( 1 ).
The combined exhausts and the sprayed water mists flow concurrently through the packed mixtures in the BIO-SORPTION unit ( 3 ). During this flow passage, the contaminants present in the fluid streams are transferred to the mixtures by a combined mechanism of absorption, adsorption and solubilization. This combined mechanism provides the foundation for the bio-degradation/bio-oxidation of the organic contaminants. For inorganic contaminants (if present), this mechanism provides a means for binding and stabilization such that the contaminants are retained within the BIO-SORPTION unit ( 3 ).
The following Table-1 illustrates the various sorbents, inert materials, and bio-solids present in a typical packed mixture and their functionality in the above treatment process.
TABLE 1
Part-
Sorbents/Bio-
icle
solids/Inert
Size
Functionality
A.
Natural zeolite,
2-4
Adsorbs light VOCs and light hydrocarbons. Binds (ion-
e.g.,
mesh
exchanges) ammonia and heavy metals present in the fluid
clinoptilolite,
streams. Increases bed utilization, and aids in microbial
mordenite,
growth and bio-oxidation. Increases bed porosity and reduces
chabazite, etc.
pressure drop.
B.
Cracked walnut
2-4
Absorbs light hydrocarbons, oils and greases, and provides
shell
mesh
extended surface areas for microbial contact and growth.
Increases bed porosity and reduces pressure drop.
C.
Activated carbon
4-10
Adsorbs VOCs and HAPs and aids in bio-film oxidation.
of vegetable or
mesh
animal origin
D.
Crushed oyster
5-10
Provides pH buffering for the packed mixtures by slowly
shell
mesh
releasing complex calcium bearing material.
E.
Calcined expanded
2-4
An inert material, provides extended surfaces for the microbes
clay
mesh
to thrive and propagate. It also increases bed porosity and
reduces pressure drop.
F.
Composted bio-
100-
Absorbs and bio-oxidizes the organic contaminants in presence
solids (manures)
200
of moisture and micronutrients. May also provide some pH
from ruminant or
mesh
buffering for the packed material.
poultry origin
Depending on the type of contaminants, the packed mixture may be prepared by tumbling a varied ratio of the above materials. However, for a common application of treating 300 ppm of HAPs such as toluene, xylene, hexane and trichloroethylene, the composition of the packed mixture is expected to be as follows:
A. Natural zeolite
20%
B. Walnut shell
20%
C. Activated carbon
15%
D. Oyster shell
5%
E. Calcined clay
20%
F. Ruminant bio-solids
20%
100%
Before loading into the BIO-SORPTION unit ( 3 ), the above materials are premixed with hydrotropic surface active ingredients or surfactants such as DOWFAX hydrotrope. The surfactants are particularly important for the treatment of hydrophobic contaminants [light hydrocarbons, chlorinated organics], where the contaminant water solubilities are increased. An increase in the contaminant solubility increases the efficiency of the sorption process, thus increasing the bio-oxidation/bio-degradation efficiency as well.
The treated exhaust stream exits the BIO-SORPTION unit ( 3 ) along with the treated wastewater converted to the form of water vapor or humidity. The exit humidity of the exhaust is monitored and controlled by a controller (HIC), which controls the pressure pump ( 6 ). Any condensate generated within the BIO-SORPTION unit ( 3 ) is collected by transfer pump ( 8 ) and returned to tank ( 1 ).
Should the BIO-SORPTION unit ( 3 ) loose microbes or require a specific culture for bio-oxidation, tank ( 4 ) and pump ( 5 ) provide a mechanism for adding microbes or cultures to the stages within the BIO-SORPTION unit ( 3 ). The mechanism can also be used for addition of micronutrients to the stages, if it is so desired.
The AGB Process is shown to be effective for treatment and degradation of a wide variety of organic pollutants such as; alcohols, esters, aldehydes, ketones, aromatics, substituted aromatic and chlorinated compounds. Many of the pollutants that the AGB Process treat fall within the category of HAPs and VOCs. The AGB Process can also treat and degrade the light and middle distillate petroleum hydrocarbons, many of which are also listed VOCs. Table-3 and Table-4 show typical performance data for the AGB Process.
Table-4 essentially indicated that one stage of the BIO-SORPTION treatment can reduce the VOC concentration by over 90%. Table-3 shows that multistage BIO-SORPTION can remove and convert the HAPS with over 99% efficiency.
The reduction in off gas emissions and corresponding reductions in wastewater contaminants, as shown in Table-5, reflects more than a mere transfer of contaminants to the sorption materials. The sorption materials provide an environment where microorganisms can colonize the substrate and use the contaminants as a carbon or other metabolic source as evidenced by the formation of CO 2 measured in the exit stream (Table-3). In effect, the present invention first sequesters contaminants from the waste streams and secondly biologically oxidizes the contaminants to nonhazardous constituents.
Applicants' process and apparatus makes use of low-cost, readily obtainable sorption materials to achieve the contaminant removal and destruction. As many variations and modifications of applicants' invention will be apparent upon a reading of the disclosure and preferred embodiment, such variations and modifications fall within the spirit and scope of the invention as measured by the following appended claims.
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An integrated treatment process and apparatus is provided for removing selected contaminants from both liquid and gaseous waste streams. A multistage separation and bio-oxidation substrate is provided in a column through which the contaminants are passed. The substrate components provide absorption, adsorption, ion exchange, solubility, and bio-degradation qualities to the column to effectively separate and destroy a wide range of contaminants in industrial waste streams.
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TECHNICAL FIELD
[0001] The present invention relates to ligands of dyes, in particular of organometallic dyes, that can be used as sensitizers. Furthermore, the present invention relates to the field of photoelectric conversion devices, in particular dye-sensitized solar cells (DSC).
PRIOR ART AND THE PROBLEM UNDERLYING THE INVENTION
[0002] The use of conventional fossil fuels as energy resource poses well-known environmental problems, as well as problems of shortage in the medium to long term. In order to solve the approaching energy crisis, a variety of attempts have been performed. Among the available alternatives, the solar energy, used in photovoltaic cells, is almost unlimited and environment-friendly compared to other forms of energy. The silicon solar cell dominates the photovoltaic business due to the high light-to-electricity conversion efficiency and due to the fact that the technology developed for many decades, is mature. However, silicon solar cells suffer from the disadvantages of a high cost of the production process, expensive raw materials and the difficulty of further increasing the efficiency of the cells.
[0003] Dye sensitised solar cells (DSCs) make use of photosensitive dye molecules (sensitizers) and transition metal oxides, which perform the functions of absorbing visible light, producing electron-hole couples, and transporting the electron produced by light absorption, respectively. DSCs have many advantages, such as high efficiency, low production cost, low energy consumption during manufacturing, and environmental friendly production. These properties have given these cells high prospects in the photovoltaic business. In 1991, Prof. Michael Grätzel at the École Polytechnique Fédérale de Lausanne developed a technological breakthrough in these cells. Since then, DSCs have gradually become a research topic of high interest in the field of solar cells (Nature 1991, 353, 737).
[0004] The dyes used as sensitizers in DSCs are key elements and have a significant impact on stability as well as the device performance, in particular the efficiency. DSCs based on bipyridine ruthenium dyes have been developed significantly (P. Wang, C. Klein, R. Humphry-Baker, S. M. Zakeeruddin and M. Grätzel, J. Am. Chem. Soc., 2004, 127, 808.).
[0005] In view of the above, it is an objective of the present invention to provide dyes that are useful as sensitizers in DSCs, and which improve device characteristics such as conversion efficiency.
[0006] In particular, it is an objective to provide dyes having high molar extinction coefficients, thus absorbing more light per dye molecule or per molar concentration. In this way, it is hoped to convert more light of the solar spectrum into electrical energy.
[0007] It is an objective of the present invention to prepare dyes that are capable of providing a dense monolayer on the semiconductor and/or photoelectrode surface of a dye-sensitized solar cell. A dense arrangement of the dye molecules on said surface is expected to increase light absorption and reduce the risk of corrosion and other kind of abrasion of the semiconductor and/or photoelectrode surface. In general, it is an objective to increase long term stability of the solar cell. A dense arrangement of dye molecules also allows a reduction of the porosity of the surface an also of the overall thickness of the semiconductor layer at the photoanode,
[0008] Another objective to provide a dye that, when absorbed on a semiconductor is capable of a absorbing as much light of the solar spectrum as possible. In particular, it is an objective to provide dyes that exhibit a pronounced red-shift when absorbed on the photoelectrode and/or semiconductor surface. It is an objective to provide a dye absorbing more photons in the red spectrum of light.
[0009] Generally, it is an objective of the present invention to provide dyes having an increased propensity of arranging and/or being adsorbed on a semiconductor and/or photoelectrode surface of a dye-sensitized solar cell in a manner that positively affects the characteristics of the device, such as conversion efficiency, for example. In other words, it is an objective to judiciously arrange of dye molecules on the photoanode surface by the molecular designing of the structures of such dyes.
[0010] Generally, the present invention addresses the objectives of providing new dyes with low production cost, and high stability, resulting in photovoltaic conversion devices having improved characteristics, such as high energy conversion efficiency.
[0011] The present invention addresses the problems depicted above.
SUMMARY OF INVENTION
[0012] The present inventors provide novel compounds useful in the preparation of dyes, as well as the dyes comprising these compounds as ligands. Remarkably, the dyes obtained according to the invention have high molar extinction coefficients. The compounds disclosed are useful in the preparation of sensitizing dyes of DSCs.
[0013] Surprisingly, it is observed that the dyes of the present invention show a particularly pronounced strong red-shift response when absorbed on the photoelectrode surface, typically a TiO 2 surface. In this way more light in the red spectrum of solar light can be utilized for the generation of electricity.
[0014] Furthermore, without wishing to be bound by theory, a high degree in stacking is observed with the dyes of the present invention when absorbed on a photoelectrode and/or semiconductor surface. Accordingly, dye molecules are absorbed in a very densely and tightly, in an ordered arrangement. In the ordered arrangement, dye molecules are arranged next to each other with aromatic rings of the antenna ligand of the dyes being in a π-stacked, superimposed relationship. In this way, a particularly dense arrangement is obtained, which further increases light absorption per surface area.
[0015] Without wishing to be bound by theory, the inventors believe that the π-stacking interaction can be positively influenced by using, in the antenna ligand (also known as ancillary ligand) a system of condensed rings, such as condensed thiophene rings. For example, by using a bipyridine ligand substituted with a substituted thieno[3,2-b]thiophenyl, the planarity of the ligand is increased and a increased stacking can be obtained. A dense layer obtained by π-stacking may also be obtained with antenna ligands based on a bipyridine substituted with chains of aromatic rings comprising and not comprising heteroatoms. Due to the dense stacking of the dye molecules on the photoelectrode and/or semiconductor surface, the thickness of the dye-carrying layer and/or the porosity can be reduced while still maintaining a high light absorption.
[0016] Accordingly, in an aspect, the present invention provides bipyridine compounds, which are substituted with one or more aromatic hydrocarbons comprising at least one heteroatom.
[0017] According to another aspect, the present invention provides compounds of formula (1):
[0000]
wherein
R 1 represents a group which comprises one or more aromatic hydrocarbon moieties selected from the group of moieties of formulae (2) to (33), and preferably (2)-(13), or a combination of two or more thereof:
[0000]
wherein, if R 1 comprises only the moiety (3), n for (3) is ≧2, and for all other R 1 and with all other combinations of moieties (2)-(33) n is ≧1;
wherein A represents O or S; B represents O or S, the said A and B being selected independently one from the other, with the proviso that in a compound where R 1 is only (2), n is 1 and R 2 is alkyl, A is O;
wherein, in moiety (28), X is selected from any one of C, Si, Ge, Sn or Pb;
wherein substituents R 2 represent, independently, hydrogen (H), halogen, hydroxyl, sulfhydryl, nitryl (—CN), cyanate, isocyanate, amine, acyl, carboxyl, sulfinyl, alkyl, alkenyl, alkynyl, and aryl, wherein said alkyl, alkenyl, alkynyl may be linear, branched or cyclic, and
wherein said amine, acyl, carboxyl, sulfinyl, alkyl, alkenyl, alkynyl, and aryl may be further substituted, and wherein one or more carbon atom, for example one or more methylene carbon atom, in said alkyl, alkenyl, alkynyl, and aryl may be replaced by any heteroatom and/or group selected from the group of —O—, —C(O)—, —C(O)O—, —S—, —S(O)—, SO 2 —, —S(O) 2 O—, —N═, —P═, —NR′—, —PR′—, —P(O)(OR′)—, —P(O)(OR′)O—, —P(O)(NR′R′)—, —P(O)(NR′R′)O—, P(O)(NR′R′)NR′—, —S(O)NR′—, and —S(O) 2 NR′, with R′ being H, a C1-C6 alkyl, optionally partially or totally perfluorinated, and/or a phenyl, or a monocyclic aromatic heterocycle, optionally partially or totally perfluorinated;
wherein Ar is a substituted or unsubstituted ar-diyl devoid of any heteroatom; Preferably, Ar comprises from 6 to 25 carbon atoms; Preferably, Ar represents a substituted or unsubstituted phenylene;
wherein R 3 to R 24 represent, independently, hydrogen (H), hydroxyl, alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, aralkyl, alkylthio, alkyl halide or halogen; and,
wherein carbon atoms at positions 3, 3′, 5, 5′ and 6, 6′ of the 2,2′-bipyridine structure of formula (1) may be further substituted, said further substituents being defined, independently, as substituents R 2 and its preferred substituents, and more preferably as substituents R 3 -R 24 and preferred substituents.
[0029] In the compounds of formula (1) above, in case two moieties carrying substituent's with identical substituent number, for example a compound comprising moieties (2) and (26) or (2) and (32), both carrying a substituent R 3 (and also a substituent R 4 ), said identically numbered substituents may be the same or different. For example, on R 3 of (2) may be hydrogen and R 3 on (26) in the same compound and even in the same R 1 may be methyl.
[0030] According to another aspect, the present invention provides the use of the compound of the invention as a ligand in an organometallic compound, as a ligand in a dye, as a ligand in a sensitizing compound, and/or as a ligand in a metal-containing sensitizing dye.
[0031] In further aspects, the present invention provides the use of the compounds of the invention as a structural component of a dye and/or as structural a component of an organometallic compound. The invention also provides the use of the compounds of the invention as a structural component of a dye of a dye-sensitized photoelectric conversion device.
[0032] In yet another aspect, the present invention provides a dye of formula (35):
[0000] ML 1 L 2 (L 3 ) 2 (35)
[0000] wherein:
M is a metal atom selected from Ru, Os, Ir, Re, Rh, and Fe; L 1 is a ligand selected from the compounds of the present invention; L 2 is an anchoring ligand; L 3 is a spectator ligand.
[0037] The invention also provides the use of the dyes of the invention as a sensitizer in a dye-sensitized photoelectric conversion device.
[0038] The dyes of the present invention have several advantages. Their production cost is low, they are obtained in high yield and are easy to purify. Furthermore, the molecular design of the dyes of the invention can be easily modified. In particular, the position of R 1 can be easily varied by using the disclosed moieties (2)-(33), preferably (2)-(13), and by selecting any combination comprising two or more of these moieties. More than 85% absorbed light-to-electricity conversion efficiency and higher than 10% overall cell (energy) conversion efficiency are achieved when the exemplary dyes are used as sensitizers in DSCs. The said dyes have thus a good light-to-electricity conversion performance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0039] FIG. 1 shows the photocurrent action spectrum of a DSC sensitized with the ruthenium dye (40) according to the present invention.
[0040] FIG. 2 shows the current density-voltage characteristics of a DSC with the ruthenium dye (40) according to the present invention.
[0041] FIG. 3 shows the photocurrent action spectrum of a DSC sensitized with the ruthenium dye (41) according to the present invention.
[0042] FIG. 4 shows the current density-voltage characteristics of a DSC with the ruthenium dye (41) according to the present invention.
[0043] FIG. 5 shows the photocurrent action spectrum of a DSC sensitized with the ruthenium dye (44) according to the present invention.
[0044] FIG. 6 shows the current density-voltage characteristics of a DSC with the ruthenium dye (44) according to the present invention.
[0045] FIG. 7 is a schematic representation of a DSC with a dye according to the present invention.
[0046] FIG. 8 is a schematic representation of the light adsorption layer 3 shown in FIG. 7 , comprising a semiconductor nanoparticle layer 4 and a dye layer 5 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0047] The present invention relates to bipyridine compounds, which are substituted with one or more aromatic hydrocarbons comprising at least one heteroatom. The aromatic hydrocarbon is preferably a further substituted or unsubstituted aryl. According to an embodiment, the heteroatoms provided in said aromatic hydrocarbon are selected from S and O.
[0048] The aryl is preferably an aromatic heterocycle or a system of two, three, four or more fused rings, at least one of which is an aromatic ring comprising at least one heteroatom. In the compound of formula (1), the moiety R 1 represents the aromatic hydrocarbon, of which the moieties of formulae (2)-(33) represent preferred embodiments.
[0049] The substituents of the bipyridine compounds of the invention, that is, any entity —R 1 -R 2 , preferably has from 4-50 carbon atoms and 1-30 heteroatoms, more preferably 4-35 carbons and 1-20 heteroatoms, and most preferably 6-25 carbons and 1-10 heteroatoms. Preferred heteroatoms are selected from halogen, Se, O and S, more preferably from O and S.
[0050] In a specific moiety (2)-(33) of the compounds of formula (1) according to the invention, A and B may be the same (both O or both S) or different (one O and one S). Preferably, A and B are different, meaning that when A is an oxygen atom, B is a sulphur atom and when A is sulfur, B is oxygen.
[0051] In an embodiment, in a compound of formula (1) where R 1 is only moiety (2) and R 2 is as defined herein, A is O.
[0052] In the substituent R 2 of the compound of formula (1) above, it is indicated that said amine, acyl, carboxyl, sulfinyl, alkyl, alkenyl, alkynyl, and aryl may be further substituted. Further substituents may be selected from C1-10 alkyl, C2-10 alkenyl, C2-10 alkynyl, which again may be linear, branched or cyclic, and from a mono- or bicyclic C6-C15 aryl. At a carbon atom, further substituent's may also be selected from hydroxyl, sulfhydryl, nitryl, cyanate, and isocyanate. Any alkyl, alkenyl, alkynyl and aryl (also the one of R 2 , not considering the further substituent) may or may not be partially or totally halogenated.
[0053] Preferably, any alkyl, alkenyl and/or alkynyl mentioned herein is linear or branched.
[0054] According to a preferred embodiment, substituents R 2 represent, independently, hydrogen (H), alkyl, alkoxy, cycloalkyl, alkyl halide, halogen, heterocycle,
[0000]
[0000] with n≧0; and,
R 3 to R 24 represent, independently, hydrogen (H), hydroxyl, alkyl, cycloalkyl, alkoxy, aryloxy, aralkyl, alkylthio, alkyl halide or halogen.
[0055] According to an embodiment, the compound of the present invention is selected from a compound of any one of formula (I)-(V) below:
[0000]
[0000] wherein R 2 is as defined above.
[0056] According to an embodiment of the compounds of the invention, R 2 comprises from 0-25 carbons and from 0-10 heteroatoms. Preferably, R 2 comprises from 1-15 carbons and from 0-5 heteroatoms, more preferably 1-10 carbons and 0-3 heteroatoms, wherein heteroatoms are defined as above for the moiety —R 1 , —R 2 .
[0057] According to a preferred embodiment, —R 2 is an alkyl, an alkenyl, an alkynyl or an aryl, in particular an alkyl, an alkenyl, or an alkynyl.
[0058] The compounds of the invention are useful in the preparation of dyes, organometallic compounds and/or of sensitizers. The compounds thus preferably form a structural component of such dyes, organometallic compounds and/or sensitizers, respectively. Preferably, the bipyridine compounds of the invention are used as ligands in dyes, organometallic compounds and/or sensitizers. The dyes, organometallic compounds and/or sensitizers comprising the compounds of the invention may, in turn, be used in photoelectric conversion devices. They may in particular be used as sensitizing dyes in such devices, for example.
[0059] The present invention relates to dyes of formula (35):
[0000] ML 1 L 2 (L 3 ) 2 (35),
[0000] wherein L 1 is a compound according to the invention.
[0060] According to a preferred embodiment, M is Ru (ruthenium).
[0061] L 2 is an anchoring ligand, which has the purpose of anchoring the dye of formula (35) on a surface of choice. Accordingly, the anchoring ligand comprises a structural unit suitable for binding to the metal M and one, two or more anchoring groups. The skilled person will thus select the binding unit and the anchoring group in dependence of the surface to which the overall dye is to be anchored.
[0062] According to an embodiment, the anchoring ligand L 2 is a bi-pyridine compound of formula (36):
[0000]
[0000] wherein R 30 and R 31 are independently one from the other selected from H, alkyl, alkenyl, alkynyl, aryl, said alkyl, alkenyl and/or aryl being substituted or unsubstituted, and from anchoring groups which may, for example, be selected from —COOH, —PO 3 H 2 , —PO 4 H 2 , —SO 3 H 2 , SO 4 H 2 , —CONHOH − , acetylacetonate, deprotonated forms of the aforementioned, and chelating anchoring groups with Π-conducting character; with the proviso that at least one of the substituents R 30 and R 31 comprises an anchoring group.
[0063] According to an embodiment, one or both of R 30 and R 31 can be an alkyl, alkenyl, alkynyl and/or aryl which is substituted with an anchoring group as cited above, for example.
[0064] According to another embodiment, L 2 is a bi-pyridine ligand of formula (37)
[0000]
[0000] wherein A 1 and A 2 are optional and, if present, are independently selected from an aromatic mono- or bicyclic ring system optionally comprising one or more heteroatoms, and R 32 and R 33 are independently selected from H and from the anchoring groups —COOH, —PO 3 H 2 , —PO 4 H 2 , —SO 3 H 2 , SO 4 H 2 , —CONHOH − , acetylacetonate, deprotonated forms of the aforementioned, and chelating anchoring groups with Π-conducting character; provided that at least one of R 32 and R 33 is an anchoring group. A 1 and A 2 may thus be absent, in which case at least one anchoring group, R 32 and/or R 33 , is connected directly to the bipyridine structure of formula (37). Examples for the moieties A 1 and A 2 , if present, are phenyl and thiophene.
[0065] Examples of chelating anchoring groups with Π-conducting character are oxyme, dioxyme, hydroxyquinoline, salicylate, and α-keto-enolate groups.
[0066] According to an embodiment, the present invention provides organometallic compounds selected from the compounds (40)-(44) below:
[0000]
[0067] The present invention relates to the use of dyes and/or organometallic compounds as defined herein as a sensitizer in a dye-sensitized photoelectric conversion device.
[0068] The present invention relates to photoelectric conversion devices. The photoelectric conversion device is preferably a photovoltaic cell, in particular a solar cell, capable of converting electromagnetic radiation, in particular visible, infrared and/or UV light, in particular sunlight, into electrical current. According to a preferred embodiment, the photoelectric conversion device is a dye-sensitized conversion device, in particular a dye-sensitized solar cell (DSC). The meanings of the terms “dye”, “sensitizer”, “sensitising dye” and “dye sensitizer” may partially or totally overlap with each other.
[0069] The present invention relates to a photoelectric conversion device comprising a compound, an organometallic compound, a dye, and/or a sensitizer of the invention.
[0070] For the purpose of illustration, an exemplary, non-limiting embodiment of a DSC according to the invention is shown in FIGS. 7 and 8 . The device comprises a light absorption layer 3 comprising a semiconductor material 4 and, absorbed thereto, a layer 7 comprising a dye according to invention or a dye comprising the compound of the invention.
[0071] According to a preferred embodiment, the semiconductor material 4 comprises a porous structure. The porous structure is illustrated by the zigzag line in FIG. 8 .
[0072] The device of the invention preferably further comprises at least one substrate 1 , an electrode 2 and a counter electrode 7 , and a charge transport layer 6 , said charge transport layer being provided between said counter electrode and said dye layer 5 .
[0073] The substrate layer 1 is preferably a transparent substrate layer selected from glass or plastic. Although there are two, a top and a bottom substrate layer 1 shown in FIG. 7 , devices with only one, a top or a bottom transparent substrate layer are also encompassed. Generally, the substrate is then on the side of the counter electrode 7 . Exemplary plastic substrates are polyethylene terephthalate, polyethylene naphthalate (PEN), polycarbonate, polypropylene, polyimide, 3-acetyl cellulose, and polyethersulfone (PES).
[0074] The conductive layer 2 may be provided by of one of Indium tin oxide (ITO), tin oxide fluoride (FTO), ZnO—Ga 2 O 3 , ZnO—Al 2 O 3 , tin-oxide, antimony tin oxide (ATO) and zinc oxide, for example.
[0075] The device of the present invention comprises a semiconductor layer ( 4 ). This layer may be constituted by a single layer or by several layers, generally has an overall thickness of up to 100 μm, for example up to 60 μm. However, according to an embodiment of the present invention, the device of the invention comprises a layer 4 comprising a semiconductor material, wherein said semiconductor layer has a thickness of smaller than 20 μm. The semiconductor layer 4 with a thickness of smaller than 20 microns may also consist of a single layer or comprise two or more separate layers, for example sub-layers. For example, the sub-layers are arranged one above the other, each sub-layer being in continuous contact with the respective one or two neighboring sub-layers. For example, the semiconductor layer may comprise a base semiconductor layer having a comparatively low porosity and thereon a comparatively high porosity semiconductor layer, wherein the sensitizers will preferably or to a larger extent be absorbed on the semiconductor material in the high porosity sub-layer. In other words, the different layers may have different porosity, for example they may be prepared from nanoparticles of different size, but preferably the sizes remain in the ranges given further below. The thickness of the entire semiconductor layer, including all potential sub-layers, is preferably <20 μm, more preferably ≦17 μm, even more preferably ≦15 and most preferably ≦13 μm.
[0076] The semiconductor material layer 4 may comprises a semiconductor material selected from Si, TiO 2 , SnO 2 , ZnO, WO 3 , Nb 2 O 5 , and TiSrO 3 , which all are exemplary semiconductor materials for the purpose of the invention. Preferably, the semiconductor material layer 4 comprises a porous layer made of semiconductor nanoparticles, for example nanoparticles made of the semiconductor materials above. The average diameter of the semiconductor nanoparticles preferably lies in the range of 0.5 nm-2000 nm, preferably 1-1000 nm, more preferably 2-500 nm, most preferably 5-100 nm.
[0077] The dye is provided in the form of a dye layer 5 , which comprises dye molecules according to the present invention, in particular dyes comprising a compound as defined by formula (1), and/or dyes as defined by formula (35), for example the exemplary dyes according to formulae (40)-(44). The dye molecules are preferably anchored by way of their anchoring group on the surface of the porous nanoparticle layer 4 and form a monomolecular layer thereon.
[0078] The charge transport layer 6 preferably comprises (a) an electrically conductive hole and/or electron transporting material or (b) an electrolyte. If the charges are transported by said electrically conductive hole and/or electron transporting material, electrons and/or holes move by electronic motion, instead of diffusion of charged molecules. Such electrically conductive layers are preferably based on organic compounds, including polymers. Accordingly, layer 6 may be an electron and/or hole conducting material. U. Bach et al. “Solid-state dye-sensitized mesoporous TiO 2 solar cells with high photon-to-electron conversion efficiencies”, Nature, Vol. 395, Oct. 8, 1998, 583-585, disclose the amorphous organic hole transport material 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9′-spirofluorene (OMeTAD) in dye-sensitised solar cells. In WO2007/107961, charge transporting materials, which are liquid at room temperature and their application in dye-sensitized solar cells are disclosed. These materials may be used, for example, for the purpose of the present invention.
[0079] If the charge transport layer is an electrolyte, which is preferred, it comprises a redox-couple. Preferred examples of redox couples suitable for dye sensitized solar cells are the I—/I 3 — couple or the SeCN—/Se(CN) 3 — redox couple.
[0080] The electrolyte preferably comprises one or more ionic liquids. Ionic liquids are generally defined by the fact that they have a melting point of 100° C. or lower. For example, anions of suitable ionic liquids may be selected from I − , Br − , Cl − , [N(CN) 2 ] − , [N(SO 2 CF 3 ) 2 ] − , [PF 6 ] − , [BF 4 ] − , [NO 3 ] − , [C(CN) 3 ] − , [B(CN) 4 ] − ,[CF 3 COO] − , [ClO 4 ] − , [BF 3 CF 3 ] − , [CF 3 SO 3 ] − , [CF 3 F 2 SO 3 ] − , [CH 3 H 2 SO 3 ] − , [(CF 3 SO 2 ) 2 N] − , [(C 2 H 5 SO 2 ) 2 N] − , [(CF 3 SO 2 ) 3 C] − , [(C 2 F 5 SO 2 ) 3 C] − , [(FSO 2 ) 3 C] − , [CH 3 CH 2 OSO 3 ] − , [CF 3 C(O)O] − , [CF 3 CF 2 C(O)O] − , [CH 3 CH 2 C(O)O] − , [CH 3 C(O)O] − , [P(C 2 H 5 ) 3 F 3 ] − , [P(CF 3 ) 3 F 3 ] − , [P(C 2 H 4 H)(CF 3 ) 2 F 3 ]] − , [P(C 2 F 3 H 2 ) 3 F 3 ] − , [P(C 2 F 5 )(CF 3 ) 2 F 3 ] − , [P(CF 3 ) 3 F 3 ] − , [P(C 6 H 5 ) 3 F 3 ] − , [P(C 3 H 7 ) 3 F 3 ] − , [P(C 4 H 9 ) 3 F 3 ] − , [P(C 2 H 5 ) 2 F 4 ] − , [(C 2 H 5 ) 2 P(O)O] − , [(C 2 H 5 ) 2 P(O)O 2 ] 2− , [PC 6 H 5 ] 2 F 4 ] − , [(CF 3 ) 2 P(O)O] − , [(CH 3 ) 2 P(O)O] − , [(C 4 H 9 ) 2 P(O)O] − , [CF 3 P(O)O 2 ] 2− , [CH 3 P(O)O 2 ] 2− , [(CH 3 O) 2 P(O)O] − , [BF 2 (C 2 F 5 ) 2 ] − , [BF 3 (C 2 F 5 )] − , [BF 2 (CF 3 ) 2 ] − , [B(C 2 F 5 ) 4 ] − , [BF 3 (CN)] − , [BF 2 (CN) 2 ] − , [B(CF 3 ) 4 ] − , [B(OCH 3 ) 4 ] − , [B(OCH 3 ) 2 (C 2 H 5 )] − , [B(O 2 C 2 H 4 ) 2 ] − , [B(O 2 C 2 H 2 ) 2 ] − , [B(O 2 CH 4 ) 2 ] − , [N(CF 3 ) 2 ] − , [AlCl 4 ] − and [SiF 6 ] 2− .
[0081] Cations of ionic liquids according to the invention may, for example, be selected from compounds having structures as shown below:
[0000]
H, provided that at least one R linked to a heteroatom is different from H;
a linear or branched C1-C20 alkyl;
a linear or branched C2-C20 alkenyl, comprising one or several double bonds;
a linear or branched C2-C20 alkynyl, comprising one or several triple bonds;
a saturated, partially or totally unsaturated C3-C7 cycloalkyl;
a halogen, preferably fluoride or chloride, provided that there is no halogen-heteroatom bond;
NO 2 , provided that there is no bond of this group with a positively charged heteroatom, and that at least one R is different from NO 2 ;
CN, provided that there is no bond of this group with a positively charged heteroatom and that at least one R is different from CN;
wherein the R may be the same or different;
wherein pairs of R may be connected by single or double bonds;
wherein one or several R may be partially or totally substituted with halogens, preferably —F and/or —Cl, or partially with —CN or —NO 2 , provided that not all R are totally halogenated;
and wherein one or two carbon atoms of any R may or may not be replaced by any heteroatom and/or group selected from the group of —O—, —C(O)—, —C(O)O—, —S—, —S(O)—, SO 2 —, —S(O) 2 O—, —N═, —P═, —NR′—, —PR′—, —P(O)(OR′)—, —P(O)(OR′)O—, —P(O)(NR′R′)—, —P(O)(NR′R′)O—, P(O)(NR′R′)NR′—, —S(O)NR′—, and —S(O) 2 NR′, with R′ being H, a C1-C6 alkyl, optionally partially or totally perfluorinated, and/or a phenyl, optionally partially or totally perfluorinated.
wherein any R is independently selected from H and C1-C15 alkyl.
[0093] Preferred substituents of the organic cations shown above are disclosed in WO2007/093961, on pages 5-7. The preferred cations defined on these pages are entirely incorporated herein by reference. The most preferred substituents R are independently selected from H and C1-C15 alkyl. Substituents are selected so that indicated positive charge is obtained.
[0094] Any alkyl, ankenyl or alkynyl referred to in this specification may be linear, branched or cyclic. Linear alkyls, alkenyls and alkynyls are preferred.
[0095] The electrolyte of the device of the invention may comprise two or more ionic liquids. Preferably, the electrolyte is substantially free of a solvent. Substantially free of a solvent means that there is less than 5 vol. % of added solvent, preferably no added solvent.
[0096] The counter electrode 7 is may comprise or consist of Pt, Au, Ni, Cu, Ag, In, Ru, Pd, Rh, Ir, Os, C, conductive polymer or a combination comprising two or more of the aforementioned. Examples of conductive polymers from which a suitable counter electrode material may be selected are polymers comprising polyaniline, polypyrrole, polythiophene, polybenzene and acetylene.
[0097] According to a preferred embodiment, the present invention provides a DSC comprising one or two transparent substrate layers 1 , a conductive layer 2 , a light absorption layer 3 , a charge transport layer 6 and counter electrode 7 . Said conductive layer 2 , said light absorption layer 3 , said electrolyte layer 6 and said counter electrode 7 are preferably connected in order, for example between two transparent substrate layers 1 . The said light absorption layer 3 comprises a semiconductor nanoparticle layer 4 and a dye layer 5 . The said semiconductor nanoparticle layer 4 is preferably connected with the said conductive layer 2 and the said dyes layer 5 is connected with the said charge transport layer 6 .
[0098] The mentioned applications, patents, and publications in the context are listed and incorporated as references in the presented specification. It is supposed that technicians in this field can use the above description within the most extensive scope. Therefore, the optimal embodiment and examples are merely considered as an exemplary illustration and are in no way meant to constitute a restriction in any way.
[0099] The following examples are used for exemplary describing the preparation and synthesis of the compounds, organometallic compounds, dyes and/or sensitizers of the present invention. It does not mean that the scope of the invention is limited to these methods and applications.
EXAMPLES
Example 1
The Synthesis of Bipyridine Ligands
1. The synthesis of 4,4′-bis(5-hexylfuran-2-yl)-2,2′-bipyridine (L1)
[0100] 2-Hexylfuran was synthesized according to a literature method (Sheu, J.-H.; Yen, C.-F.; Huang, H.-C.; Hong, Y.-L. V. J. Org. Chem. 1989, 54, 5126). 2-Hexylfuran (2.20 g, 14.45 mmol) was dissolved in 40 mL of anhydrous THF and cooled to −78° C. After addition of n-butyllithium (Aldrich) (6.90 mL, 2.5 M in hexane, 17.34 mmol), the solution was stirred under Ar at −78° C. for 1 h. The mixture was stirred for 3 h at 20° C. and then cooled to −78° C. Tributylstannyl chloride (6.12 g, 18.80 mmol) in 10 mL of anhydrous THF was added dropwise via a syringe and stirred for 2 h at −78° C. The mixture was stirred overnight at room temperature. The reaction mixture was quenched with aqueous NH 4 Cl and extracted with CH 2 Cl 2 . The combined organic layers were dried over MgSO 4 . After the removal of solvent, the unpurified 2-hexyl-5-tributylstannylfuran (4.22 g, 9.55 mmol) and 4,4′-dibromo-2,2′-bipyridine (1.00 g, 3.18 mmol) were dissolved in 120 mL of DMF. A catalytic amount of Pd(PPh 3 ) 2 Cl 2 (0.13 g, 0.16 mmol) was added and the reaction mixture was stirred at 85° C. under Ar overnight. After the removal of DMF, the resulting solid was passed through a silica gel column using CHCl 3 as eluent to afford L1 (1.12 g, 77% yield) as yellowish solid. 1 H NMR (600 MHz, CDCl 3 , δ H ): 8.66 (dd, J) 5.2 Hz, J) 0.6 Hz, 2H), 8.61 (s, 2H), 7.54 (dd, J) 5.2 Hz, J) 1.6 Hz, 2H), 6.93 (d, J) 2.8 Hz, 2H), 6.13 (d, J) 3.2 Hz, 2H), 2.72 (t, J) 7.6 Hz, 4H), 1.75-1.67 (m, 4H), 1.44-1.31 (m, 12H), 0.90 (t, J) 7.0 Hz, 6H). MS (EI) m/z calcd for (C 30 H 36 N 2 O 2 ), 456.62. found, 456.
2. The synthesis of 5-octylthieno[3,2-b]thiophene
[0101] To a stirred solution of thieno[3,2-b]thiophene (10.7 mmol) in anhydrous CH 2 Cl 2 (200 mL) was added octanoyl chloride (11.0 mmol). The mixture was stirred for 30 min at room temperature, cooled to 0° C., and AlCl 3 (12.0 mmol) was added portionwise. The mixture was then warmed to 25° C. and stirred overnight. The reaction was quenched by the addition of water and acidified with a 2 M HCl aqueous solution. The mixture was extracted with CH 2 Cl 2 . The organic layers were washed with water and dried over MgSO 4 . After the removal of solvent, the crude product was purified by column chromatography (CH 2 Cl 2 /n-hexane: 1/1) on silica gel to afford 1-(thieno[3,2-b]thiophen-2-yl)octan-1-one (2.08 g) as milk white solid. Yield: 72%. 1 H NMR (400 MHz, CDCl 3 , TM H ): 7.90 (s, 1H), 7.61 (d, 1H), 7.30 (d, 1H), 2.92 (t, 2H), 1.81 1.74 (m, 2H), 1.37 1.30 (m, 8H), 0.88 (t, 3H). Cold anhydrous ether (100 mL) was added to separate batches of LiAlH 4 (58.0 mmol) and AlCl 3 (13.5 mmol) and the resulting suspended solutions were carefully mixed. To this mixture was added 1-(thieno[3,2-b]thiophen-2-yl)octan-1-one (6.0 mmol) in dry ether at 0° C. The mixture was warmed to room temperature and then stirred for 3 h. The reaction was quenched by the careful addition of ether and a 2 M HCl aqueous solution. The gray precipitate was filtrated and washed with ether. The combined filtrate was extracted, washed with water, and dried over MgSO 4 . After rotary evaporation of solvent, the crude product was purified with column chromatography (n-hexane) on silica gel to afford white solid. (1.46 g). Yield: 96%. 1 H NMR (400 MHz, CDCl 3 , TM H ): 7.27 (d, 1H), 7.18 (d, 1H), 6.95 (s, 1H), 2.87 (t, 2H), 1.73 1.53 (m, 2H), 1.39 1.27 (m, 10H), 0.88 (t, 3H).
3. The synthesis of 4,4′-bis(5-octylthieno[3,2-b]thiophen-2-yl)-2,2′-bipyridine (L2)
[0102] n-Butyllithium (6.94 mmol) was slowly added dropwise to a solution of 5-octylthieno[3,2-b]thiophene (5.94 mmol) in anhydrous THF at 78° C. under Ar. The mixture was stirred at this temperature for 30 min and then for 1.5 h at room temperature followed, after cooling to 78° C., by the addition of tributylstannyl chloride (7.52 mmol). After stirring for 4 h at room temperature, the reaction was terminated by adding a saturated NH 4 Cl aqueous solution. The mixture was extracted with CH 2 Cl 2 and dried over MgSO 4 . After the removal of solvent, the crude tributyl(5-octylthieno[3,2-b]thiophen-2-yl)stannane (5.2 mmol) was mixed with 4,4′-dibromo-2,2′-bipyridine (1.72 mmol) in 150 mL DMF. The catalyst Pd(PPh 3 ) 2 Cl 2 (0.08 mmol) was added to the solution and the mixture was heated at 85° C. under Ar overnight. After the removal of DMF, the resulting solid was purified by column chromatography on silica gel using CHCl 3 as eluent to afford an ivory white solid. Yield: 74%. 1 H NMR (400 MHz, CDCl 3 , TM H ): 8.73 (s, 2H), 8.67 (d, 2H), 7.84 (s, 2H), 7.52 (d, 2H), 6.99 (s, 2H), 2.90 (t, 4H), 1.76 1.72 (m, 4H), 1.41 1.28 (m, 20H), 0.89 (t, 6H). MS (EI) m/z calcd. for C 38 H 44 N 2 S 4 : 657.03. Found: 657.24.
Example 2
Synthesis of Dyes According to the Invention
[0103]
[0104] The synthetic approach for the preparation of the dyes of the present invention is illustrated by scheme 1 above, which will be used to describe in more detail the synthesis of dye (40) according to the present invention.
[0105] Compound 1a is obtained from Aldrich. Compound 1b corresponds to ligand L1 obtained in Example 1 (1.) above.
[0106] Compounds 1a (0.1 g, 0.16 mmol) and 1b (0.146 g, 0.32 mmol) were dissolved in DMF (50 mL). The reaction mixture was heated to 60° C. under nitrogen for 4 hours with constant stirring. To this reaction flask 4,4′-dicarboxylic acid-2,2′-bipyridine (0.08 g, 0.32 mmol) was added and refluxed for 4 hours at 140° C. Then an excess of NH 4 NCS (0.89 g, 13 mmol) was added to the reaction mixture and the reflux was continued for another 4 hours at the same temperature. The reaction mixture was cooled down to room temperature and the solvent (DMF) was removed by using a rotary evaporator under vacuum. Water was added to the flask and the insoluble solid was collected on a sintered glass crucible by suction filtration, washed with water and EtO 2 , and dried under vacuum. The crude was dissolved in a basic methanol solution (NaOH) and purified by passing through a column. After the collecting main band was concentrated, the pH was lowered to 4.8 by titration with dilute nitric acidic in methanol solution, which produced dye 20 as a precipitate. The precipitate was collected on a sintered glass crucible by suction filtration and dried in air. The following NMR data for dye 40 (with double sodium salt form) were obtained: 1 H NMR (400 MHz, DMSO-d6): δ=0.83 (t, 3H), 0.89 (t, 3H), 1.26-1.42 (m, 12H), 1.62 (m, 2H), 1.75 (m, 2H), 2.70 (t, 2H), 2.83 (t, 2H), 6.41 (d, 1H), 6.53 (d, 1H), 7.28 (d, 1H), 7.37 (d, 1H), 7.43 (d, 1H), 7.61 (d, 1H), 7.87 (d, 1H), 8.06 (d, 1H), 8.32 (d, 1H), 8.70 (s, 1H), 8.86 (s, 1H), 8.94 (s, 1H), 9.10 (s, 1H), 9.13 (s, 1H), 9.45 (d, 1H).
[0107] The dyes of formulae (41)-(44) were synthesized using corresponding starting materials instead of 1b according to an analogues procedure. For example, by using the octylthieno[3,2-b]thiophen bipyridine ligand (L2) obtained in Example 1 (3.) above, instead of L1 of Example 1, dye (41) of the present invention is obtained.
Example 3
Preparation of a Dye-Sensitized Solar Cell Using the Sensitizing Dye of Formula (40)
[0108] A screen-printed double layer film of TiO 2 particles was used as photoanode. A 7 μm thick film of 20 nm sized TiO 2 particles was first printed on the fluorine-doped SnO 2 conducting glass electrode and further coated by a 5 μm thick second layer of 400 nm sized light scattering anatase particles. Fabrication procedure for nanocrystalline TiO 2 particles and photoanode with nanostructure double layers of TiO 2 has been reported. (Wang P. et al., Enhance the Performance of Dye-Sensitized Solar Cells by Co-grafting Amphiphilic Sensitizer and Hexadecylmalonic Acid on TiO 2 Nanocrystals, J. Phys. Chem. B., 107, 2003, 14336).
[0109] The TiO 2 electrodes were immersed into a solution containing 300 μM of dye (40), and, in another device, dye (41), in tent-butanol and acetonitrile (volume ratio 1:1) for 16 h.
[0110] Surprisingly, the dye molecules of the present invention, when absorbed on the TiO 2 exhibit a particularly pronounced red-shift, substantially increasing the spectrum of the light absorbed by the light-absorbing surface (here: TiO 2 and absorbed dye). This substantial increase in the red shift could not be expected from the light absorption spectrum of the dyes e in solution.
[0111] It is also derived that dye molecules are particularly densely arranged on the semiconductor surface. In conclusion, π-stacking of the dyes of the invention when absorbed on the surface explains the strong high absorption of light in the red part of the light spectrum and of the dense arrangement of dye molecules.
[0112] The double layered, nanocrystalline TiO 2 film electrode was assembled with a thermally platinized conducting glass electrode. The two electrodes were separated by a 35 μm thick hot-melt ring and sealed up by heating.
[0113] The internal space was filled with an electrolyte consisting of: 1.0 M 1,3-dimethylimidazolium iodide, 0.05 M LiI, 0.1 M guanidinium thiocyanate, 30 mM I 2 , 0.5 M tert-butylpyridine in the mixture of the solvents acetonitrile and valeronitrile (85/15, v/v). After that, the electrolyte-injection hole was sealed. For the fabrication details see the reference of Wang P. et al., “A Solvent-Free, SeCN − /(SeCN) 3 − Based Ionic Liquid Electrolyte for High-Efficiency Dye-Sensitized Nanocrystalline Solar Cell”, J. Am. Chem. Soc., 126, 2004, 7164.
[0114] The short circuit photocurrent density (J sc ), open circuit photovoltage (V oc ), and fill factor (ff) of the device with dye (20) under AM 1.5 full sunlight (100 mW/cm 2 ) are 17.8 mA cm −2 , 725 mV, and 0.734, respectively, yielding an overall conversion efficiency (η) of 9.5%.
[0115] Further dye-sensitized solar cells were fabricated according to the method of Example 2, and the device characteristics are listed in Table 1 below.
[0000]
TABLE 1
Photovoltaic device parameters of
DSCs According to the Invention
Short-circuit
photocurrent
Conversion
Open-circuit
density
Fill factor
efficiency
dye
photovoltage(mV)
(mA/cm 2 )
ff
(%)
40
725
17.80
0.734
9.5
41
760
17.87
0.776
10.5
44
728
18.33
0.752
10.0
[0116] With the other exemplary dyes (42) and (43) of the present invention, devices with similar and performance are obtained.
[0117] Without wishing be bound by theory, it is believed that the particularly positive results obtained with dye (41) is due to the increased π-stacking of the dye on the surface of the photoanode, which in is due to the high planarity of the bipyridine antenna ligand substituted with a substituted condensed system of thiophene rings. The present invention thus provides ways of increasing the propensity of dye molecules to arrange in an advantageous way on the semiconductor and/or photoelectrode surface.
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The present invention relates to novel compounds that are useful as ligands in organometallic dyes. More particularly, the invention relates to dyes comprising the compounds, said dyes being sensitizing dyes useful in solar cell technology. According to an embodiment, the present invention discloses new ruthenium dyes and their application in dye-sensitized solar cells (DSC). The referred ruthenium dyes with new structural features can be easily synthesized, show more than 85% light-to-electricity conversion efficiency and a higher than 9% cell efficiency.
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BACKGROUND AND SUMMARY OF THE INVENTION
The invention relates to a cable clamp terminal for the connection of conducting cables to an electrical apparatus for instance to a circuit interrupter having a terminal block with two superposed housings or sockets, each of them disposed to receive the end of a cable and two set screws likely to be screwed into a tapped aperture of said block crosswise extending to said housings. The intermediate one of the screws tightens the cable inserted in the lower housing between the bottom and the intermediate screw and the other upper one tightens the cable inserted in the upper housing between the intermediate screw and the upper screw.
For certain applications it is necessary to connect to each terminal of an electrical apparatus, in particular of a high power circuit breaker with moulded casing, two cables or conducting wires. A connector in the form of a conducting block fastened on the connection lug of the circuit breaker and showing two juxtaposed holes meant for receiving connection cables was already suggested. The width of this terminal is too big for modern circuit breakers with moulded casing, and to remedy to this disadvantage, a superposed arrangement of two connecting cables was provided, for instance in the circuit breaker according to U.S. Pat. No. 3,355,685. In this case, it is necessary to provide an intermediate setscrew inserted between the two cables, to ensure a proper electrical connection between the cables and the terminal. The terminal being fastened to the circuit breaker lug, the lower cable was first introduced and the intermediate screw tightened wedging this cable against the terminal bottom. The second cable was then introduced and the upper screw comes and wedges the cable between the two screws. After mounting the intermediate screw is no longer accessible and it is then impossible to verify the right tightening of cables or to carryout a retightening taking up a certain stress relief or compression of the cable strands.
An object of the present invention is to remedy to this disadvantage and to permit the realization of a terminal of reduced width for the connection of two superposed conducting cables allowing a later retightening when the cables become loose in their sockets.
According to the present invention, the tapping of the intermediate screw shows a longitudinal play or clearance allowing a limited axial sliding of the intermediate screw fixed in rotation.
The tapping with play or clearance advantageously extends all along the length of the tapped aperture, the corresponding axial play of the two screws having no effect on the upper screw. The threading is advantageously of the square thread type to reduce in addition the side stresses exerted upon the terminal block.
BRIEF DESCRIPTION OF THE DRAWINGS
Other advantages and technical data will more clearly appear from the following description, wherein reference is made to the accompanying drawings, in which:
FIG. 1 is an elevational view, partially cut-away, of a terminal according to the invention, fastened on an electrical apparatus lug;
FIG. 2 is a partial section according to the line II--II on FIG. 1, a single cable and the associated setscrew being mounted; and
FIGS. 3 and 4 are sections according to the line II--II, showing the terminal after the two cables mounting and after retightening respectively.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the figures, a block 10 of a connection terminal in the general form of a parallelipiped shows an elongated slot 11 crossing through and through the block 10. Connections terminals 10 are mounted at opposite ends of the base of a molded-case circuit breaker of the type disclosed in U.S. Pat. No. 3,355,685. The slot 11 width is slightly superior to the cross-section of the cables 18, 20 to connect, the height or length of the slot 11 being sufficient to insert the ends of the two superposed cables 18, 20. The bottom 12 of the block 10 is built on to and fastened on the upper side of an electrical apparatus lug 14 by a fixing bolt 16. The slot 11 extends parallel to the lug 14 and a tapped hole 22, of the block 10, extends perpendicular to the slot 11 according to the longitudinal axis of the block represented on FIG. 1 by the line II--II. The tapped hole 22 opens on the upper side 24 of the block 10 and extends at its base by a reduced cross-section aperture 23 for the passage of the bolt 16. The tapped hole 22 receives two threaded setscrews, an intermediate screw 26 and an upper screw 28. The intermediate screw splits the housing formed by the slot 11 in a lower housing or socket receiving the cable 20 end and in an upper housing admitting the cable 18 end up. The threading of the hole 22 and screws 26, 28 is of the square thread type, the height h of the thread being notably inferior to half of the thread pitch p so as to obtain a notable clearance allowing an axial sliding or back-lash of the screws 26, 28 without rotation of these last ones. The screws 26, 28 show on their upper side an hexagonal recess 30 for inserting a tightening tool and on their lower side a pivot 32 to penetrate between the strands 34 of the cables 18, 20.
The connection is made in the following way:
The block 10 is fastened on the lug 14 by the bolt 16 inserted through the aperture 22. The end of the lower cable 20 is then inserted through the slot 11 and the intermediate screw 26 is screwed into the tapped hole 22 up to the tightening with compression of the strands 34 of the cable 20 (see FIG. 2). The upper cable 18 is inserted inside the slot 11 above the intermediate screw 26 and tightened by the upper screw 28 screwed inside the tapped hole 22. Referring to FIG. 3, it can be seen that the cable 18 is tightened between the screws 26, 28, and that under the tightening effect the screw 26 has been axially shifted creating a relatively weak play j 1 at the level of the threading. After a certain development time during which the apparatus went through repeated thermal cycles and some compression of the cable strands, a retightening is done by causing the upper screw 28 to rotate. The retightening effect is transmitted to the intermediate screw 26 which undergoes an additional sliding resulting in a play J 2 of a value superior to the one of play j 1 . It is easy to understand that the screw 28 rotation ensures a retightening of the two cables 18, 20 owing to the possibility of axial sliding of the intermediate screw 26 (FIG. 4).
As an advantage the block 10 is made of a moulded conducting material and the tapping with play 22 advantageously extends all along the height of the hole. It is clear that the upper screw 28 does not need a mounting with play and that the realization of a terminal inside which only the intermediate screw 26 has the possibility of axially sliding will still be part of the invention. The invention also applies to terminals capable of receiving a greater number of superposed conductors.
The principles, preferred embodiments and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein should not, however, be construed as limited to the particular forms disclosed, as these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the present invention. Accordingly, the foregoing detailed description should be considered exemplary in nature and not as limiting to the scope and spirit of the invention as set forth in the appended claims.
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The invention relates to a terminal likely to receive two superposed conductors or cables. Between the cables is inserted an intermediate setscrew likely to shift axially by being fixed in rotation so as to transmit to the lower cable a retightening stress exerted by rotation of the upper screw after some development time.
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[0001] This application claims priority from Provisional Application No. 60/686,048, filed Jun. 1, 2005, the entire content of which is incorporated herein by reference.
TECHNICAL FIELD
[0002] The present invention relates, in general, to intimal hyperplasia, and, in particular, to a method of inhibiting intimal hyperplasia using siRNA to E2F. The invention further relates to compounds and compositions suitable for use in such a method.
BACKGROUND
[0003] One method for specifically inhibiting gene expression is via delivery of short interfering RNAs (siRNAs). Among the approaches for gene inhibition, including anti-sense oligodeoxynucleotides (ODNs) and ribozymes, siRNA is currently the fastest developing approach for gene inhibition, target validation, and therapeutic applications 1 . siRNAs appear to be well-suited for therapeutic application. In addition to their highly specific inhibition of a target gene, siRNAs are effective at low concentrations, thus reducing or eliminating the likelihood of toxicity due to non-specific activity. Recently, several proof-of-principle studies have demonstrated the therapeutic potential of siRNAs. These have included treatments for hepatitis 2,3 , viral infections 4,5 , macular degeneration 6 , sepsis 7 , tumor growth and invasiveness 8-10 , chronic neuropathic pain 11 , and serum cholesterol 12 . What is evident from these studies is that targeting siRNAs to particular cell types or delivering them locally further reduces the likelihood of detrimental side effects while increasing the efficiency of the siRNA response. Currently, there is an intensive effort to discover methods for chemical modifications of siRNAs that will further facilitate target delivery as well as increase stability of functional siRNAs in vivo l2,13 .
[0004] These targeted methods for silencing of specific genes with siRNAs make for attractive therapeutic strategies in the treatment of localized pathological intimal hyperplasia. Pathological intimal hyperplasia occurs in venous by-pass grafts and in arteries following injury incurred during by-pass grafting or angioplasty and is in large part due to the proliferation of vascular smooth muscle cells (VSMCs) in the media and their migration into the intima of the treated vessel 14,15 . Such proliferation is induced by a number of growth stimulatory signals that are activated by vascular injury 16-18 . In addition to increased proliferation, apoptosis of cells in the media leading to inflammation and upregulation of chemokines and their receptors has also been shown to play a role in priming this hyperproliferative response 19,20 . Such abnormal behavior of vascular cells leads to high long-term failure rates of by-pass surgery and angioplasty for treatment of cardiovascular disease. Indeed, despite refinements in surgical procedures, the rate of vein graft failures remains high 21,22 . These failures often require repeated treatment by surgery or angioplasty and can result in heart attack or amputation of ischemic organs. Accordingly, development of molecular strategies that effectively inhibit such pathogenic cellular processes has been the focus of much research and many clinical trials over the past 20 years.
[0005] The E2F family of transcription factors plays a pivotal role in controlling the expression of genes involved in DNA replication, cell cycle progression, and cell fate determination 23-28 . To date, eight gene products (E2Fs 1-8) comprise the E2F family of proteins and additional isoforms for E2F3 and E2F6 also exist though their functions have not been well characterized 29-32 . Based on sequence homology, the E2F proteins can be divided into three distinct categories. E2Fs1-3 are tightly regulated during the cell cycle and function mostly as activators of transcription 26 . E2F4 and E2F5 function as transcriptional repressors in concert with pRb family members, p130 and p107 33 . E2F6-8 are believed to function as repressors of transcription independent of the pRb family of proteins 30,31,34 . In addition, evidence from various groups suggests that the activator E2Fs (E2F1-3) have specific functions. This functional specificity is most evident in a role for E2F3 in control of cell proliferation and a role for E2F1 in the induction of apoptosis 35,36 .
[0006] Because E2F activity plays a central role in controlling cell growth and cell fate determination, inhibition of E2F activity promises to be an effective way to block the cellular processes in vascular smooth muscle cells (VSMCs) associated with pathological intimal hyperplasia. Indeed, recent studies by Eckhart et al. 40 demonstrated that intimal hyperplasia is greatly reduced in damaged arteries in E2F3 knockout mice.
[0007] The present invention results from studies designed to test the ability of siRNAs selectively targeting E2Fs, E2F1 and E2F3 to inhibit proliferation and apoptosis of VSMCs in vitro, as well as for their ability to reduce the development of intimal hyperplasia in a mouse bypass graft model. The invention provides a method of inhibiting pathological intimal hyperplasia that occurs, for example, in venous by-pass grafts and in arteries following injury resulting from by-pass grafting or angioplasty.
SUMMARY OF THE INVENTION
[0008] The present invention relates, in general, to intimal hyperplasia, and, in particular, to a method of inhibiting intimal hyperplasia using siRNA to E2F. The invention further relates to compounds and compositions suitable for use in such a method.
[0009] Objects and advantages of the present invention will be clear from the description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIGS. 1A-1D . Effect of siRNAs against E2F1 and E2F3 on E2F-mediated transcriptional activity. ( FIG. 1A ) NIH3T3 cells were transfected with E2F1-luc reporter plasmid along with an HA-E2F1 expression vector alone or together with synthetic siRNA duplexes against E2F1 (F1-2, F1-3, F1-4, F1-5) or E2F3 (F3-2). ( FIG. 1B ) NIH3T3 cells were transfected with p68-luc reporter plasmid along with an HA-E2F3 expression vector alone or together with synthetic siRNA duplexes against E2F3 (F3a-2, F3-2, F3-5, F3-6) or E2F1 (F1-3). Luciferase activity was normalized to Renilla activity from three independent experiments. Mouse vena cava vascular smooth muscle cells (VSMCs) were transfected using a lipid base reagent with either a non-specific control siRNA (control) or siRNAs to either: ( FIG. 1C ) E2F1 (F1-2, F1-3, F1-4, F1-5) or ( FIG. 1D ) E2F3 (F3-2, F3-5, F3-6). The siRNAs were transfected either alone or together (siE2F3 pool, siE2F1 pool). Nuclear extracts from transfected cells were then resolved on SDS acrylamide gels and assessed for presence of E2F proteins by Western blotting with specific antibodies (top panels). Target specificity for each individual siRNA was assessed by determining the levels of a non-target E2F member (bottom panels).
[0011] FIGS. 2A-2C . Lack of different E2Fs can reduce or accelerate growth of VSMCs in vitro. ( FIG. 2A ) Mouse vena cava VSMCs were transfected with either a non-specific control siRNA (scr) or siRNAs to either E2F1 (F1-3, F1-4, F1-5) alone or along with an E2F1 rescue construct that generated a mutant transcript that was not degraded by its target siRNA, F1-3 (Rescue). Cells were then synchronized at the 01/S boundary by addition of 0.5 μM hydroxy urea (HU). After 21 h cells were released from the HU block and stimulated to reenter the cell cycle by addition of media containing serum and 3 H-thymidine. 24 h post serum addition cells were lysed and analyzed for 3 H-thymidine incorporation using a scintillation counter. ( FIG. 2B ) Mouse vena cava VSMCs were transfected with either a non-specific control siRNA (scr) or siRNAs to either E2F3 (F3-2, F3-5, F3-6) alone or along with an E2F3 rescue construct that generated a mutant transcript that was not degraded by its target siRNA, F3-6 (Rescue). ( FIG. 2C ) VSMCs from vena cavae of WT or E2F4−/− mice transfected as described above.
[0012] FIG. 3 . Lack of E2F1 can reduce apoptosis of VSMCs in vitro. Mouse vena cava VSMCs were transfected with either a non-specific control siRNA (scr), siRNAs to either E2F1 (F1-3) or E2F3 (F3-2, F3-6), or F1-3 along with the E2F1 rescue construct. 24 h post transfection, cells were treated with 100 μM cisplatin for 30 h. Cells were then fixed and stained for active caspase 3 using a PE-conjugated antibody specific to cleaved caspase 3. Flow cytometric analysis was used to quantitate % PE positive cells.
[0013] FIGS. 4A-4D . Uptake of siRNAs in venous grafts in vivo. ( FIG. 4A ) Schematic of experimental approach for assessing delivery of siRNAs in grafted vessels. ( FIG. 4B ) Assessment of siRNA stability. Three venous grafts of WT mice were incubated with 32 P-scrambled siRNA for 30 min at 25° C. Following incubation the grafts were washed perfusedly, freeze-thawed twice to break up the tissue, and the siRNA extracted using phenol:chlorophorm. The labeled siRNA was subsequently resolved on a non-denaturing acrylamide gel to assess extent of degradation. ( FIG. 4C ) Assessment of siRNA uptake. The vena cavae were excised from mice and incubated either at room temperature or on ice in DMEM containing a total of 5 nmoles scrambled siRNA and trace amounts (100,000 cpms) of end-labeled 32 P-scrambled siRNA for 30 minutes. The vessels were then washed profusedly before quantitating uptake of 32 P-scrambled siRNA into the vessels. The % uptake was measured by dividing the amount of 32 P within the vessels by the input (100,000 cpms) 32 P-scrambled siRNA X 100. ( FIG. 4D ) E2F protein products after siRNA treatment. Extracts of venous grafts previously incubated with either scrambled siRNA (SCR) or siRNAs to E2F1 and E2F3 (siE2Fs) were resolved on SDS-PAGE and proteins subsequently transferred onto PVDF membrane for immunoblotting.
[0014] FIGS. 5A-5C . siRNAs against E2F1 and E2F3 reduce intimal hyperplasia in venous by-pass grafts. ( FIG. 5A ) Photomicrographs showing cross-section from murine vein-graft 28 days after implantation treated with (left) pluronic gel alone (Gel control), (middle) non-specific scrambled siRNA (SCR), and (right) siRNAs against E2F1 and E2F3 (siE2F). The venous VSM intimal hyperplasia in the Gel control and SCR treated 28 day graft is highly cellular and composed of smooth muscle cells interspersed in a connective tissue matrix. The vessel wall of the siE2F 28 day graft is only a few cell layers thick. (Modified Masson trichrome and Verhoeff elastin stain). (FIG. 5 A′) 40 × magnifications of boxed regions in FIG. 5A showing thickness of intimal layer. ( FIG. 5B ) Mice treated with either no siRNAs (Gel; pluronic gel control), 5 nmoles of control siRNA (SRC), or 2.5 nmoles each of siRNAs against E2F1 and E2F3 ( 2 ′ 0 H siRNA). Area of the intimal layer (Intima) and medial layer (Media) of the vessel are represented. The intimal ratio (area of the intima of the vessel divided by the total area of the vessel) was determined 28 days post-bypass graft. ( FIG. 5C ) Data in FIG. 5B was plotted as % Inhibition, where the gel control group is set to 100% Inhibition of intimal hyperplasia. Each bar represents an average measurement from 13 mice. Intimal Ratio is reduced by ˜42% after treatment with the siRNAs against the E2Fs; P<0.0001. Intimal thickness is reduced by ˜0.44%, P=0.0003, no significant change in Medial thickness is observed; P=0.8727.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The discovery that small interfering RNAs (siRNAs) can inhibit gene expression in a sequence-specific manner in mammalian cells has raised the possibility of treatments for many pathological conditions using such gene inhibitors in vivo. It is shown in the Example that follows that siRNA to E2F1 and E2F3 can inhibit the proliferation and apoptosis of venous primary smooth muscle cells in culture. Moreover ex vivo delivery of these siRNAs to vein grafts results in silencing of the endogenous E2F genes following surgical implantation of the grafts in the mouse. Importantly, administration of siRNAs specific to these growth-promoting E2Fs significantly reduced intimal hyperplasia in the implanted grafts. These studies establish the therapeutic proof of principal that siRNAs can limit intimal hyperplasia in bypass grafts in animals. Thus the E2F specific siRNAs represent lead compounds that may prove useful for inhibiting this pathological process and graft failure following peripheral and coronary bypass graft surgery in man.
[0016] Described herein is the development of siRNAs that act as selective inhibitors of the activator E2Fs. The data presented in the Example that follows show that these inhibitors can be effectively delivered to the target site for therapeutic purposes. Specifically, it is shown that short-term, local delivery of siRNAs targeting the growth promoting E2Fs (E2F1 and E2F3) results in reduced intimal hyperplasia following vein bypass grafting in the mouse. The reduction in intimal hyperplasia correlated with the ability of these siRNA inhibitors to block proliferation and apoptosis of vena cavae VSMCs in culture. It is not surprising, given the dual role of E2F1 in the control of cell proliferation and cell fate, that inhibition of cell proliferation was achieved with siRNAs against either E2F1 or E2F3, while inhibition of DNA-damage induced apoptosis was specific to the siRNA against E2F1. The development of molecular strategies that inhibit both pathological cellular proliferation and apoptosis leading to intimal hyperplasia has been the focus of much research 37,39,42,43 . Indeed, recent reports have suggested that, in addition to increased proliferation, apoptosis of cells in the media following vascular damage may be involved in priming the hyperproliferative response associated with intimal hyperplasia in vivo 19 . Because E2F activity is capable of mediating proliferation of cells as well as apoptosis depending on presence or absence of growth stimulatory signals or in response to DNA damage 36,44 , inhibition of E2F activity promises to be an effective way to block the cellular processes in VSMCs.
[0017] Strikingly, it was observed that the E2F3 siRNAs are only effective at inhibiting VSMC proliferation when E2F4 is present. E2F3 siRNAs are much less effective inhibitors of cell proliferation in VSMCs derived from vena cava of E2F4 knockout mice ( FIG. 2C ). This result suggests that E2F3 and E2F4 play opposing roles in VSMC proliferation and is consistent with the recent observation that mice lacking E2F4 (a growth arresting E2F) exhibit increased intimal hyperplasia following arterial damage, while mice lacking E2F3 (a growth promoting E2F) show reduced intimal hyperplasia compared to WT control mice 40 . Similarly, mice lacking E2F1 also show a stark reduction in intimal hyperplasia under these experimental conditions. Together, these studies provide strong evidence to suggest that agents such as siRNAs that specifically block only the proliferative and apoptotic functions of the E2Fs would be most effective for limiting restenosis in the clinic. Moreover, they indicate that inhibitory agents that do not distinguish between the various E2F family members, for example ones that inhibit both E2F3 and E2F4 function, will likely be sub-optimal agents for controlling vascular smooth cell proliferation and intimal hyperplasia in the clinic. Consistent with this interpretation, two large randomized phase 3 studies recently demonstrated that a non-selective E2F inhibitor, an E2F DNA decoy, did not significantly impact on intimal hyperplasia and graft failure 45 . Thus one explanation for the lack of clinical efficacy of the E2F DNA decoy, which bears the consensus E2F DNA binding site for all the E2Fs, is that since the DNA decoy can inhibit the activity of both growth stimulating E2Fs and growth repressing E2Fs then its administration may result in a phenotype similar to the one observed when E2F3 siRNAs are not very effective at inhibiting cell proliferation when E2F4 activity is absent.
[0018] Although technical challenges are still associated with the therapeutic application of siRNAs, such as specificity, cost of synthesis, delivery, and stability, siRNAs are the fastest developing therapeutic approach for gene inhibition. In the therapeutic setting of bypass surgery, many of these hurdles appear to be surmountable. The likelihood of the siRNAs having non-specific toxicity do to non-specific effects on other mRNAs is greatly reduced because the siRNAs are directly and transiently delivered to by-pass grafts ex vivo which should greatly reduce the potential systemic toxicity. To that effect, it has been shown that the siRNAs against the E2Fs are specific for the targeted E2Fs ( FIGS. 1C and 1D ). Moreover, the delivery of siRNA to grafts ex vivo will substantially the quantity of the siRNA required for treatment and thus reduce the cost of their use in this clinical setting. In addition, currently intensive work is also being performed further increase stability and facilitate cellular delivery and tissue bioavailability of siRNAs 6,10,12,13 . These improvements in the siRNA technology should also facilitate their use in the setting of cardiac and vascular surgery. Thus, it is anticipated that the clinical utility of siRNAs will be evaluated in the setting of cardiovascular surgery in the near future.
[0019] Certain aspects of the invention can be described in greater detail in the non-limiting Example that follows.
Example
Experimental Details
[0020] Unless otherwise noted, all chemicals were purchased from Sigma-Aldrich Co., all restriction enzymes were obtained from New England BioLabs, Inc. (NEB), and all cell culture products were purchased from Gibco BRL/Life Technologies, a division of Invitrogen Corp.
Cell Culture
[0021] Primary mouse embryonic fibroblasts (MEFs) were maintained at 37° C. and 5% CO 2 in Dulbecco's modified Eagle's medium (DMEM) supplemented with 10% heat inactivated fetal bovine serum. Primary cultures of mouse VSMCs from thoracic aortas were obtained and cultured as described previously 47,48 . VSMC from aorta of wild type and E2F4−/− mice were maintained in 4-10 Medium.
Luciferase Assays
[0022] NIH/3T3 cells were maintained in DMEM supplemented with 10% fetal bovine serum (Gibco). 5×10 4 cells/well were seeded in 24-well plates 16 h prior to transfection. Co-transfection of siRNA and reporter plasmids was carried out using Superfect (Qiagen) following the manufacturer's protocol as previously described 49 . Per well, 1 pg of either E2F1-Luc or p68-Luc, 1 ng pRL-TK (Promega), and where indicated, 4 ng of HA-E2F1 or HA-E2F3, and 50 pmoles siRNA duplex were used with a final volume of 360 μl. 24 h post transfection cells were assayed for Luciferase and Renilla expression. Each experiment was performed in triplicate.
Nuclear Extracts and Westerns
[0023] Primary, passage 3, VSMCs from vena cava of wildtype mice were seeded in 60 mm dishes at 50% confluency and transfected twice using Superfect Reagent (Qiagen) with either 1 μM of scramble siRNA (control), 1 μM siRNA against E2F3 (F3-2 alone, F3-5 alone, F3-6 alone, or a combination of F3-1, F3-5, F3-6 (siE2F3 pool), or 1 μM siRNA against E2F1 (F1-5 alone, F1-4 alone, F1-3 alone, F1-2 alone, or a combination of F1-5, -4, -3, -2 (siE2F1 pool)). The first transfection was performed 24 h after seeding the cells while the second transfection was performed 48 h after seeding the cells. This transfection protocol allows for increased transfection efficiencies under these conditions. Cells were allowed to recover for 24 h after the second transfection and then assayed for E2F1 or E2F3 protein expression levels. Nuclear extracts of vena cava VSMCs were prepared as previously described 49 . Extracts were resolved on SDS-PAGE and proteins subsequently transferred onto PVDF membrane for immunoblotting. The following primary antibodies were employed for immunoblotting: anti-E2F3a (SantaCruz, SC-879), anti-E2F1 (SantaCruz, SC-251), anti-E2F2 (SantaCruz, SC-633), and anti-E2F4 (SantaCruz, SC-1082).
Generation of Mutant E2F Constructs for Use in Rescue Experiments
[0024] The siRNA target sequences are as follows: F1-3, AAGAUCUCCCUUAAGAGCAAA and F3-6, AAGACUUCAUGUGUAGUUGAU.
[0025] E2F mutants (pcDNA3-HAE2F1 mut and pcDNA3-HAE2F3amut) were generated using standard molecular biology techniques. Briefly, the primers used for the mutagenesis are as follows:
[0000]
E2F1,
5′-atggttatggtgatcaaagc;
E2F3,
5′-atggcccactacgtgaacca,
5′-agcctcggggaggaggaaggcatcagcgatctcttcgatgcttacga
tttggaaaagctcccactggtggaagactttatgtgctcataattatgct
tcg.
[0026] E2F1 mut harbors silent point mutations that render it insensitive to the effect of siRNA F1-3. E2F3amut harbors silent point mutations designed to abrogate targeting by siRNA F3-6.
Transfection Assays
[0027] Primary, passage 3, VSMCs from vena cava of wild type or E2F4−/− mice were seeded in 60 mm dishes at 50% confluency and transfected twice with either 1 μM scrambled siRNA (control), 1 mM siRNA against E2F1 (F1-3, F1-4, or F1-5), 1 μM siRNA against E2F3 (F3-2, F3-5, or F3-6), or 1 μM of F1-3 plus 4 μg of pcDNA3-HAE2F1, or F3-6 plus 4 pg of pcDNA3-HAE2F3amut (Rescue) for 24 hr using Superfect transfection reagent (Qiagen). Cells were also transfected with an siRNA against E2F6 as a control (siE2F6). Following transfection cells were trypsinized and seeded in 12-well plates at ˜20,000 cells/well.
VSMC Proliferation (DNA Synthesis) Assay
[0028] Transfected VSMCs from vena cava of wild type and/or E2F4−/− mice were trypsinized and seeded in 12-well plates at ˜20,000 cells/well. Cells were then forced into a G1/S block by addition of 0.5 μM HU. After 21 hr cells were released from the HU block by addition of media lacking HU and incubated with media containing 3 H-thymidine (1 μCi/mL medium) to, monitor DNA synthesis. After 24 hr incubation in the presence of media containing 3 H-thymidine cells were washed twice with PBS, washed once with 5% w/v trichloroacetic acid (TCA) (VWR cat# VW3926-2), were collected in 0.5 mL of 0.5N NaOH (VWR cat# VW3221-1) and placed in scintillation vials for measurement of 3 H-thymidine incorporation. Data were plotted as % Cell Proliferation where 100% Cell Proliferation is defined by % 3 H-thymidine incorporation. 3 H-thymidine incorporation for Gel Control was set to 100%.
VSMC Apoptosis Assay
[0029] Transfected VSMCs from vena cava of wild type mice were treated with 4-10 medium alone (WT no cisplatin) or 4-10 medium containing 100 μM cisplatin for 30 h. Cells were then fixed and stained for active caspase 3 using a PE-conjugated antibody specific to cleaved caspase 3 (as specified in manufacturer's protocol) (Pharmingen). Flow cytometric analysis was used to quantitate % PE positive cells as a measure of apoptosis. % Apoptosis is defined by % PE-Positive Cells as measured by Flow cytometric analysis.
[0000] In Vivo siRNA Up-Take Assay
[0030] The vena cavae from 3 mice per condition were excised as described below and the excised vessels incubated either at room temperature or on ice in DMEM containing a total of 1 μM scrambled siRNA and trace amounts (100,000 cpms) of end-labeled 32 P-scrambled siRNA for 30 minutes. The vessels were then washed profusely with DMEM three times and twice with PBS before quantitating uptake of 32 P-scrambled siRNA into the vessels. Uptake of 32 P-scrambled siRNA was determined by placing the vessels in scintillation fluid and measuring 32 P using a Scintillation Counter. The % Uptake was measured by dividing the amount of 32 P within the vessels by the input (100,000 cpms) 32 P-scrambled siRNA X 100. In addition, following the 30 min incubation at 25° C., the 32 P-scrambled siRNA from one of the vessels was extracted using phenol:chlorophorm and resolved on a non-denaturing acrylamide gel. To assess activity of the siRNAs in vivo, extracts of venous grafts previously incubated with either scrambled siRNA (SCR) or siRNAs to E2F1 and E2F3 (siE2Fs) were resolved on SDS-PAGE and proteins subsequently transferred onto PVDF membrane for immunoblotting. The following primary antibodies were employed for immunoblotting: anti-E2F3a (SantaCruz, SC-879), anti-E2F1 (SantaCruz, SC-251), anti-E2F2 (SantaCruz, SC-633), and anti-E2F4 (SantaCruz, SC-1082).
In Vivo Venous Mouse By-Pass Graft Model
[0031] The venous by-pass graft model in mice was performed as previously described by Zhang and Hagen et al. 50 . Briefly, a 0.8-cm segment of inferior vena cava (IVC) was harvested from a donor mouse and anastomosed to a syngeneic recipient's carotid artery. Prior to transplantation in recipient mouse, the IVC was placed in DMEM solution containing either 5 nmoles of SCR siRNA or a mixture of 2.5 nmoles each of siRNAs against E2F1 and E2F3 for 30 minutes at RT. Meanwhile, in the graft recipient mouse, a 10-mm segment of the left common carotid artery was isolated from surrounding tissues. This segment was occluded proximally and distally with 8-0 nylon sutures, two arteriotomies were created proximally and distally, about 0.8 cm apart, and the vessel was then flushed with saline. End-to-side anastomosis between the IVC and carotid was performed using two fixed sutures at the proximal and distal corners of each arteriotomy and two running sutures, each 180° around the circumference (with 4-6 bites/180°). The carotid segment between the IVC anastomoses was ligated at both ends and cut, thereby stretching the IVC graft. The 8-0 nylon ligatures were then removed and patency of the graft was determined by assessing blood flow through the wall of the satiated graft. The remaining DMEM solution containing the siRNAs was mixed with 30% pleuronic gel (BASF) on ice and transferred to the site of the transplant where the gel was allowed to polymerize. The incision was then closed and the remaining nucleic acid was allowed to diffuse out of the gel into the vein over the next few days. The whole procedure was performed strictly with atraumatic technique with a 96% success rate. Operative time averaged 10 minutes for IVC harvest and 40 minutes for carotid interposition grafting. All operative procedures were performed aseptically, with pentobarbital sodium (50 mg/kg body weight, intraperitoneal) anesthesia, using an operating microscope (WECK Model 029001, zoom 3.6-18, J. K. Hoppl Corporation).
[0032] The grafts were harvested four weeks after transplantation. The grafts were exposed through the previous incision and the thoracic cavity was opened. The right atrium was incised and the graft was perfused with PBS through the left ventricle. The grafts were then perfusion-fixed in situ with 10% buffered formalin for 20 minutes at a constant pressure of 100 mm Hg. The grafts ware excised and placed in 10% neutral buffered formalin for 24 hours and then transferred to 70% ethanol until embedding in paraffin. 5 micron serial sections every 0.5 mm with total 4 sections per graft were taken from the middle of the grafts and stained with Mikat, a modified Masson's trichrome and Verhoeff's elastic tissue stain. This staining allowed the identification of collagen as green, elastin as black, cytoplasm as red, and nuclei as black.
[0033] Morphometric analysis of tissue sections was performed using images of 40× original magnification, captured using a Nikon camera. Perimeter and area measurements for the lumen, neointima, and media were performed by plainimetry using ImageTool (Version 3.0, UTHSCSA). Neointima was identified by the criss-cross, random-appearing orientation of smooth muscle cells and by the primarily red color imparted by the prevalence of VSMC cytoplasm and relative absence of collagen. Media was recognized by the circular orientation of VSMCs and the primarily green color imparted by collagen. The measurements were used to create concentric circles of area or perimeter equivalent to the measured from the sections, and the radii of these circles were used to calculate the average thickness of each graft layer.
Statistical Analysis
[0034] These results are given as means±SE. Statistical analysis was conducted using a one-way ANOVA. A P-value of 0.05 or less was considered to indicate a significant difference. In addition to a one-way ANOVA, two-tailed unpaired t tests were conducted to compare each treatment group to every other. The siE2F group was significantly different from the SCR and gel control groups, P<0.0001. The SCR group was not significantly different from the gel control group, P>0.05.
Results
[0035] Designing and Evaluating siRNAs Against E2F1 and E2F3
[0036] To develop more potent and selective inhibitors of the human and murine growth promoting E2Fs (E2F1 and E2F3) through the use of siRNA technology mouse and human sequences were first aligned and regions of identity were considered for siRNA targeting. Selected sequences were then BLASTed to confirm E2F target-specificity and uniqueness within the human and mouse genomes and approximately six siRNAs for each E2F target were chosen for analysis.
[0037] To assess the inhibitory effects of these E2F-specific siRNAs in mouse fibroblasts in culture, transient transfection assays were performed, using lipid-based transfection reagents to measure E2F-mediated transcriptional activation. Specifically, reporter constructs containing a luciferase gene under the control of either the E2F1 or the p68 promoter were co-transfected with the E2F1 (HA-E2F1) or E2F3 (HA-E2F3) expression cassettes, respectively, in the presence or absence of siRNAs against E2F1 or E2F3 ( FIG. 1 ). The inhibitory effect of the various E2F-specific siRNAs on E2F-mediated transactivation was scored by measuring reporter activation following co-transfection of the siRNAs with their E2F counterparts and reporter constructs. It was next demonstrated by western blot analysis that transient delivery of siRNAs against E2F1, (F1-2, F1-3, F1-4, F1-5) ( FIG. 1C ) or E2F3, (F3-2, F3-5, F3-6) ( FIG. 1D ) into vena cava VSMC cells specifically reduced the expression of E2F3 and E2F1. Importantly, the siRNAs against E2F3 had no effect on E2F1 protein levels and the siRNAs against E2F1 had no effect on E2F3 protein levels. The efficiency of siRNA transfer was assessed by co-transfection of a non-specific fluorescently labeled siRNA and was determined to be >75% (data not shown). Moreover, analysis of siRNA transfected VSMCs with reduced levels of either E2F1 or E2F3 proteins resulted in significantly decreased proliferation (measured by 3 H-thymidine incorporation) of VSMCs in culture ( FIGS. 2A and B). This effect was specific to the E2F targeted and could be partially reversed by co-transfection of a gene encoding either a modified E2F1 or a modified E2F3 transcript that was not degraded by the target siRNAs (F1-3 and F3-6 respectively) (Rescue). The reason for the partial reversal is due to lower transfection efficiencies for plasmid DNA vs. siRNAs in primary VSMCs (data not shown). Importantly, the siRNA effect was greater in E2F4+/+ vena Cava VSMCs compared to vena cava VSMCs derived from E2F4−/− littermates (˜90% vs. ˜20% reduction in proliferation, respectively) ( FIG. 2C ). This observation is consistent with recent findings that reveal the opposing roles of E2F3 and E2F4 in the development of restenosis following arterial damage in vivo 40 . Specifically, it was shown that loss of E2F3 prevents the development of intimal hyperplasia, while loss of E2F4 hastens the progression of intimal hyperplasia following arterial damage. Together, these findings support the notion that “selective” E2F antagonists, such as siRNAs against the growth promoting E2Fs, E2F1 and E2F3, may prove to be more efficacious at inhibiting mammalian proliferation in vitro and in vivo than non-selective inhibitors of the entire family of E2F proteins.
[0038] Given the role of E2F1 protein in apoptosis, the effects of inhibition of E2F1 expression on cisplatin-induced apoptosis in VSMCs were assessed. Analysis of siRNA transfected vena cava VSMCs with reduced levels of E2F1 (F1-3) resulted in significantly decreased apoptosis (measured by accumulation of cleaved active caspase 3 using Flow cytometric analysis) of VSMCs in culture ( FIG. 3 ). This effect was specific to the E2F1 siRNA and could be partially reversed by co-transfection of a mutant E2F1 transcript that was not degraded by its target siRNA. Furthermore, siRNAs to E2F3 (F3-2 and F3-6) did not result in decreased apoptosis compared to scramble control (SCR) siRNA.
[0000] Uptake of siRNAs in Venous Grafts In Vivo
[0039] The main obstacle to achieving in vivo gene silencing by RNAi technologies is delivery. First, to assess stability of siRNA in the venous grafts, vena cavae were excised from three mice and incubated with a radiolabeled siRNA ( 32 P-SCR) for 30 minutes. Then total RNA was isolated from the vessels and intact siRNA was resolved on a non-denaturing PAGE gel ( FIGS. 4A and 4B ). Next, to determine efficiency of siRNA uptake in the venous grafts, excised vena cavae were incubated with the siRNA ex vivo either at room temperature to allow uptake or on ice to block active transport 41 . Grafts were then washed profusely before quantitating uptake of 32 P-siRNA into the vessels. Analysis of uptake revealed that ˜68% of the labeled siRNA had been transported into the venous grafts. In contrast, less than 5% of the input siRNA was associated with the venous grafts incubated on ice ( FIG. 4C ). It was next demonstrated by western blot analysis that delivery of siRNAs against E2F1 and E2F3 (F1-3 and F3-6 in combination) into mouse venous grafts reduced E2F1 and E2F3 protein expression 48 hours after the grafts had been implanted in mice. Importantly, F1-3 and F3-6 had no effect on the expression of other E2F family members (see E2F2 and E2F4 westerns) ( FIG. 4D ).
Reduced Intimal Hyperplasia in Mouse Venous By-Pass Grafts
[0040] The effects of the siRNAs against the growth promoting E2Fs (E2F1 and E2F3 in combination) on the development of intimal hyperplasia in a mouse model of venous by-pass grafting were next assessed. Briefly, inferior vena cava to carotid artery vein graft procedures were performed on 13 mice per experimental condition. Four weeks post-procedure the grafts were harvested, fixed, sectioned, and stained for analysis. Analysis of the graft sections confirmed that intimal hyperplasia had developed in control animals that received no treatment (Gel control), as well as in animals treated with a scrambled siRNA (SCR) (FIGS. 5 A and 5 A′). In contrast, treatment of venous grafts with siRNAs against both E2F1 and E2F3 (F1-3 and F3-6, respectively) resulted in a significant decrease in intimal hyperplasia when compared to control samples ( FIGS. 5B and 5C ). The siRNAs against the E2Fs reduced the Intimal-to-Medial Ratio by ˜42% and ˜57% and the Intimal Ratio by ˜36% and 43% when compared to both SCR control and Gel control groups, P<0.0001 ( FIG. 5C , bottom panels). By contrast, the E2F siRNAs had no significant effect on medial area ( FIGS. 5B and 5C ). In summary, the data indicate that the inhibition of E2F1 and E2F3 protein production by siRNAs significantly reduces the development of intimal hyperplasia in this mouse model of venous bypass grafting.
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34. Trimarchi J M, Fairchild B, Wen J, Lees J A. The E2F6 transcription factor is a component of the mammalian Bmi1-containing polycomb complex. Proc Natl Acad Sci USA. 98(4):1519-24 (2001).
35. DeGregori J., Leone G., Miron A., Jakoi L. and Nevins J. R. Distinct roles for E2F proteins in cell growth control and apoptosis. Proc Natl Acad Sci USA 94, 7245-50 (1997).
36. Wu X, Levine A J. p53 and E2F-1 cooperate to mediate apoptosis. Proc Natl Acad Sci USA. 91(9):3602-6 (1994).
37. Morishita, R. et al. A gene therapy strategy using a transcription factor decoy of the E2F binding site inhibits smooth muscle proliferation in vivo. Proc Natl Acad Sci USA 92, 5855-9 (1995).
38. Mann M J, et al. Genetic engineering of vein grafts resistant to atherosclerosis. Proc Natl Acad Sci USA. 92, 4502-6 (1995).
39. Mann, M J. et al. Ex-vivo gene therapy of human vascular bypass grafts with E2F decoy: the PREVENT single-centre, randomised, controlled trial. Lancet 354, 1493-8 (1999).
40. Eckhart A D, et al. E2F3 and E2F4 Exhibit Opposing Functions in Intimal Hyperplasia. Nature Med.
41. Yakubov L A, Deeva E A, Zarytova V F, Ivanova E M, Ryte A S, Yurchenko L V, Vlassov V V. Mechanism of oligonucleotide uptake by cells: involvement of specific receptors? Proc Natl Acad Sci USA. 86(17):6454-8 (1989).
42. Fulton G. J., et al. Antisense oligonucleotide to proto-oncogene c-myb inhibits the formation of intimal hyperplasia in experimental vein grafts. J. Vasc. Surg. 25, 453-463 (1997).
43. Bai H, et al. Inhibition of intimal hyperplasia after vein grafting by in vivo transfer of human senescent cell-derived inhibitor-1 gene. Gene Ther. 5, 761-9 (1998).
44. Kowalik T F, DeGregori J, Schwarz J K, Nevins J R. E2F1 overexpression in quiescent fibroblasts leads to induction of cellular DNA synthesis and apoptosis. J Virol. 69(4):2491-500 (1995).
45. Mann M. J. and Dzau V. J. Therapeutic applications of transcription factor decoy oligonucleotides. J Clin Invest 106, 1071-1075 (2000).
46. Morishita, R. Perspective in progress of cardiovascular gene therapy. J Pharmacol Sci. 95(1):1-8 (2004).
47. Chen L., Xin X., Eckhart A. D., Yang N., and Faber J. E. Regulation of vascular smooth muscle growth by α1-adrenoreceptor subtypes in vitro and in situ. JBC 270, 30980-30988 (1995).
48. Iaccarino G., Smithwick A. L., Lefkowitz R. J., and Kock W. J. Targeting Gβγ signaling in arterial vascular smooth muscle proliferation: A novel strategy to limit restenosis. Proc. Natl. Acad. Sci. USA 96, 3945-3950 (1999).
49. Giangrande P H, Hallstrom T C, Tunyaplin C, Calame K, Nevins J R. Identification of E-box factor TFE3 as a functional partner for the E2F3 transcription factor. Mol Cell Biol. 23, 3707-20 (2003).
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[0091] All documents and other information sources cited above are hereby incorporated in their entirety by reference.
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The present invention relates, in general, to intimal hyperplasia, and, in particular, to a method of inhibiting intimal hyperplasia using siRNA to E2F. The invention further relates to compounds and compositions suitable for use in such a method.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Patent Application No. 60/912,112, entitled “STRUCTURAL HEALTH MONITORING SYSTEM AND METHODS FOR USE,” filed Apr. 16, 2007, the entire disclosure of which is incorporated herein by reference.
TECHNICAL FIELD
This invention relates generally to structural health monitoring (SHM) systems. More specifically, this invention relates to the calculation of probabilistic damage sizes and placing associated upper bounds on the damage sizes calculated in such systems.
BACKGROUND
The diagnostics and monitoring of structures for damage, such as that carried out in the structural health monitoring (SHM) field, are often accomplished by employing arrays of transducers. The transducers are often used as both actuators and sensors, and typically comprise piezoelectric transducers, e.g., lead-zirconate-titanate (PZT) transducers, which are bonded to the structure to excite elastic waves at ultrasonic frequencies that propagate along paths on the surface of the structure or through the structural medium. When damage occurs on or in the structure between the transducers, the associated actuator-sensor propagation paths are affected by the damage, resulting in changes to the signals received at the sensors indicative of the location, size and type of the damage. Knowing which actuator-sensor paths are affected is useful in determining the presence of damage and the approximate location of damage. However, there may not be direct information about the size of the damage. There is a need, therefore, for a method for determining the size of the damage, as well as methods for placing probabilistic bounds on the size of the damage detected.
SUMMARY
In numerous possible SHM system embodiments, damage in a structure is detected as a crack, opening or void that interferes with the propagation of an elastic wave signal through a structure between a actuator transducer and a sensor transducer mounted thereon, thereby causing attenuation of the direct line-of-sight propagating signal wave, i.e., the first arrival signal, or alternatively, causing scattering from the damage to be detected by other sensor transducers as secondary signals. The damage may be of a type that opens to the surface of the monitored structure, in which case the preferred mode of detection is via surface propagating elastic waves, or the damage may be embedded below the surface of the structure, in which case the preferred mode of detection is via bulk propagating elastic waves. The extent of the damage, e.g., the size thereof, may be determined by the propagation paths that are directly or indirectly affected thereby, i.e., those demonstrating attenuation of the first arrival signal, and by the extent of generation of secondary signals at adjacent transducers due to scattering.
In one embodiment, a method for calculating a probable damage size in a structural health monitoring system includes defining a configuration of an array of a plurality of transducers mounted on a structure, wherein any selected pair of transducers comprises an actuator and a sensor, and wherein each pair defines a signal wave propagation path in the structure. All propagation paths that are affected by being touched by a damage of the structure, as well as all propagation paths that are untouched and thereby unaffected by the damage, are identified. A range of sizes of the damage is determined. A probability density of the damage versus damage size is calculated on the basis of the transducer array configuration and the affected and unaffected propagation paths identified. On the basis of the probability density, a most probable damage size is found, and the probabilities of the damage either being greater or less than the most probable damage size are determined.
The above and other features and advantages of the present invention will be more readily apparent from a consideration of the detailed description of some exemplary embodiments thereof set forth below, particularly if taken in conjunction with the accompanying drawings, wherein the same or like elements are referred to by the same or like reference numerals throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates an exemplary arrangement of actuator-sensor transducers and propagation paths for detecting damage, according to an embodiment of the disclosure.
FIGS. 2A through 2F illustrate how damage centers may be located as a function of damage size according to an embodiment of the disclosure.
FIG. 3 is a probability density curve of the likelihood of a damage having various sizes according to the present disclosure.
FIG. 4 is a flow diagram of a method 100 for determining the probabilistic size of damage according to the present disclosure.
DETAILED DESCRIPTION
In a typical structural health monitoring (SHM) system, an array of transducers is attached to the structure. The transducers may be capable of both transmitting and sensing elastic waves that propagate through the structure. Pairs of such actuator-sensor transducers, where an actuator transmits and the sensor receives, establish selected elastic wave propagation paths within the structure. An elastic wave may be detected by direct propagation from the actuator to the sensor. If damage occurs on this direct path, the signal may be partially or entirely attenuated. Alternatively, if the damage is not located directly in the propagation path, but is offset therefrom, the damage may nevertheless be severe enough to reflect a wave originating from an actuator, and be detected by one or more receiving sensors as a secondary signal or pulse. In this latter case, the received secondary pulse will correspond to a longer propagation path, and a consequent longer transmission time, and so may thereby be distinguished from the direct signal.
If damage has been determined to be on one or more particular actuator-sensor direct paths (i.e., “affected paths”), then the geometry of the actuator-sensor paths (both affected paths and unaffected paths) can be used to determine the size of each damage in a statistical sense. That is, for each damage, a probability density curve for the damage size can be determined, giving an upper bound on the size, as well as the most probable size thereof.
The damage may be characterized as a circle and the calculations for the damage size are based on the geometry of the actuator-sensor paths. In order to be detected via a direct propagation path, the damage must touch the affected paths, i.e., the signal amplitude may then be affected (i.e., attenuated) by the existence of damage in the path. At the same time, by definition, the damage does not touch any of the unaffected paths, thus setting an upper bound on the damage size. The determination of whether there is damage in the affected path may be based on a signal threshold requirement.
The nature of the geometry of the placement of actuators and sensors, i.e., the selected paths, determines the details of the calculation of the probabilistic damage size. FIG. 1 is an exemplary illustration of possible damage that intersects no more than two actuator-sensor paths in a square array of transducers. As above, a transducer may function as both an actuator and a sensor. That is, a transducer may both transmit and/or receive elastic waves in the structure. In the illustrated example, the transducers are arranged in a square array, and damage is presumed to intersect the two diagonal paths in a single square sub-array of transducers. That is, for the illustrated example, there are only two affected paths.
In the example of FIG. 1 , the lower bound of the damage size, i.e., the smallest possible damage size, is a zero radius point located directly at the crossing point of the affected paths. Similarly, the largest damage that intersects both paths is a circle whose diameter is nearly, but not equal to or greater than, the side dimension of the square formed by the corner locations of the transducers. It may be noted that there is only one point at which the smallest size damage can be located. Similarly, the largest size damage must be located with its center at the same point. Damage of either extreme size is possible, but highly unlikely. This may be understood from the fact that the totality of locations in which the center of damage for either the smallest or the largest damage is a single point of zero dimension. Thus, the probability of a damage of either the largest or smallest size is substantially zero. Conversely, the probability of a damage occurring which is characterized as having a certain diameter intermediate of the two extrema increases in proportion to the area in which the damage center can be located and still intersect both of the affected paths.
Thus, for such intermediate damage sizes, the circle representing the diameter of the damage may be placed with its center in locations that cover an area which is limited by the requirement that the perimeter of the damage circle always crosses both sensor-actuator paths (in this case, the diagonals) but does not intersect the respective edge paths of the four transducers located at the corners of the sub-array. This area in which the damage center may be found, divided by the area of the sub-array, is proportional to the probability that the damage has the corresponding size. FIGS. 2A-2F illustrate how changing the size of the damage affects the possible locations in which the damage may be positioned and still intersect or touch only the identified affected paths, i.e., the diagonal paths. It can be seen that the central area grows from a point to a maximum value as the damage size increases, and then shrinks again to a point, as the damage grows to the maximum possible diameter. In the example illustrated, it may be seen that the highest probability of damage size is determined approximately by the dark area of FIG. 2D .
FIG. 3 is a plot of the respective sizes of the central areas of FIGS. 2A-2F as a function of damage size, where the damage size is a continuous variable. The central area may be normalized to the size of the sub-array square dimension, and the vertical axis of FIG. 3 may thus be normalized so that the area under the curve has a total value of unity.
FIG. 3 , when normalized in this way, becomes the probability density curve. The most probable damage size is then determined at the peak, or maximum of the curve. Physically, this peak represents the largest dark central area of FIGS. 2A-2F , as described above.
In addition to the most probable damage size, the percentage chance that the detected damage is smaller or larger than the most probable size can be computed as the respective areas under the curve above or below the most probable damage size. The percentage probability that the damage is smaller than the most probable size is the area under the curve to the left of this value, and the area under the curve above the most probable size is the percentage probability of its being larger than the most probable size.
The details of calculating the probability density, most probable damage size, and probability of damage being greater or less than the most probable size are affected by the details of the sensor-actuator geometry and the structure. A variety of numerical methods and curve fitting approximations are well known in the art, and are contemplated within the scope of the disclosure.
FIG. 4 is a process flow diagram of a method 100 for determining the probabilistic size of damage for an actuator-sensor array in a SHM system. Method 100 includes specifying a configuration geometry (block 10 ) for locating transducers on the structure. After actuator-sensor propagation paths are defined, a damage location region enclosed by a selected group of transducers is identified in which the damage intersects a selected number of paths (the affected paths), and in which defined adjacent paths are not affected by the damage (block 20 ), i.e., paths adjacent to the damage, but which the damage does not touch, and therefore, does not affect.
Given the specified region in which the damage is located, a damage size may be posited that is characterized by a circle of an initial smallest radius (block 30 ) that touches all affected paths, but does not touch any defined unaffected paths. The smallest size damage then determines a lower bound of detected damage size (block 35 ). In the case of two intersecting paths, this is, by definition, a point, viz., the point of intersection of the paths. However, in some transducer arrays, it is possible that the two affected paths do not intersect, and thus, the smallest damage size may not be a point. The possible locations of the damage may be determined (block 40 ) to be a plurality of positions in which the damage touches all affected paths, but does not touch unaffected paths. The locations of the centers of all possible positions of the damage circle determines an area enclosing the centers (block 45 ) of the corresponding sized damage.
The radius of the posited damage circle may be incrementally increased by a selected amount (block 50 ). A determination is then made whether the new, larger damage circle so posited can be positioned so as to touch only the affected paths (decision block 60 ). If it is determined that the damage can be positioned in one or more locations (a “Yes” result in decision block 60 ), method 100 continues to step 40 , in which the possible locations at which the center of the new damage circle may be positioned so as to touch the affected paths previously identified without also touching the unaffected paths previously identified. A new damage area is calculated (block 45 ) which encloses the centers corresponding to the new damage size.
When the damage circle radius is iteratively increased (block 50 ) in the foregoing manner, a “No” result will eventually occur at decision block 60 , meaning that the newly incremented circle now no longer touches only the previously identified affected paths. Thus, an upper bound on the damage size is thereby determined (block 70 ), based on the last damage circle providing a Yes result in decision block 60 . The upper and lower bound on damage size, and areas enclosing the damage centers corresponding to different damage sizes are combined to calculate the probability density curve (in block 80 ) described above in connection with FIG. 3 , together with the most probable damage size (i.e., the peak or maximum of the curve), and the probabilities of the damage being either greater or less than the most probable size described above.
Although the present disclosure has been described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the art that a variety of modifications and variations may be made to these without departing from the spirit and scope of the present disclosure as defined in the appended claims, and their functional equivalents.
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A method for calculating the probable damage size in a structure includes defining a configuration of an array of transducers mounted on the structure. Any pair of the transducers includes an actuator and a sensor, and each pair defines a propagation path in the structure. All propagation paths that are affected by being touched by a damage of the structure, and all adjacent paths that are untouched and thereby unaffected by the damage, are identified. A range of sizes of the damage is determined, and a probability density of the damage versus damage size is calculated on the basis of the transducer array configuration and the affected and unaffected propagation paths identified. On the basis of the probability density, a most probable damage size is determined, and the probability of the damage being greater or less than the most probable damage size is also determined.
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BACKGROUND OF THE INVENTION
The present invention relates to methods and apparatus for making highly purified water which is beneficial for human consumption.
Although water is a vital constituent in maintaining human life, all too often, modern water supplies, even after treatment in municipal plants, are loaded with chemicals, viruses and bacteria. These impurities are present and are not conventionally thought of as harmful or disease-causing. However, the constant bombardment of the human organism and its sensitive immune system with these impurities through the consumption of water tainted with these impurities, over time, can have deleterious effects on human health.
Various attempts have been made in the past to provide water purification, including the plethora of devices and designs incorporated into municipal water treatment systems. However, none of these designs achieve a high degree of purity in the resulting water. The continued consumption of such water continues to lead to the deleterious effects noted above.
Accordingly, there is a need in the art for an improved water treatment method and apparatus for obtaining highly pure water to aid in the human condition by reducing disease and other health problems.
SUMMARY OF THE INVENTION
The present invention fulfills this need by providing an apparatus for purifying water including the following components, connected in series:
a first UV radiator to remove microbes including a helical quartz tube through which water to be purified passes and an ultraviolet light source to irradiate water passing through the helical quartz tube,
a first filtration stage including a fine filter and an ultra-fine filter,
a first reactor including a bed of coarse quartz granules, followed by a bed of noble metal,
a second filtration stage including a fine filter and an ultra-fine filter,
a second UV radiator to remove microbes including a helical quartz tube containing coarse quartz granules and through which water to be purified passes and an ultraviolet light source to irradiate water passing through the helical quartz tube,
a second reactor including a bed of noble metal followed by a bed of coarse quartz granules,
a third reactor including a bed of noble metal followed by a bed of coarse quartz granules,
a fourth reactor including a bed of coarse quartz granules,
a third filtration stage including a micro-filter,
a fourth filtration stage including a micro-filter,
a third UV radiator to remove microbes including a helical quartz tube through which water to be purified passes and an ultraviolet light source to irradiate water passing through the helical quartz tube,
a fifth filtration stage including an ultrafilter,
a fourth reactor including a bed of gold, and
an irradiation stage including a quartz tube through which water to be purified passes and a laser light source with a wavelength in the range of 200-300 nm to irradiate water passing through the quartz tube,
whereby microbes in the water passing through the apparatus are killed and removed.
In more general terms, the apparatus can be described as including a UV radiator to remove microbes including a helical quartz tube through which water to be purified passes and an ultraviolet light source to irradiate water passing through the helical quartz tube. A reactor follows, including a bed of coarse quartz granules and a bed of noble metal. A further reactor includes a bed of gold, and an irradiation stage includes a quartz tube through which water to be purified passes and a laser light source with a wavelength in the range of 200-300 nm to irradiate water passing through the quartz tube. These components work together so that microbes in the water passing through the apparatus are killed and removed.
Preferably, the apparatus includes a bottling facility for bottling the purified water in clean glass bottles including a source of ozone to blanket the interface between the purified water and atmosphere with ozone as water is being filled into the bottles.
In a less expensive form the apparatus includes a UV radiator to remove microbes including a quartz tube through which water to be purified passes and an ultraviolet light source to irradiate water passing through the quartz tube, a first filtration stage including a fine filter and an ultra-fine filter, a reactor including a bed of coarse quartz granules, followed by a bed of noble metal, and a second filtration stage including a fine filter and an ultra-fine filter. Although some purity is sacrificed, this arrangement also has the effect that microbes in the water passing through the apparatus are killed and removed.
The filters in the first filtration stage create a back-pressure on the water in the UV radiator, which coupled with heating by the ultraviolet light source, results in oscillations in the water which are destructive to the microbes.
Preferably, the UV radiator is provided with airflow passages around the quartz tube, resulting in the formation of ozone, and tubing is provided to bubble the ozone through the water.
The noble metal may be selected from the group consisting of silver, gold, platinum, palladium, ruthenium, rhodium, iridium, and osmium.
Preferably, a second UV radiator is also provided including a quartz tube containing coarse quartz granules and through which water to be purified passes and an ultraviolet light source to irradiate water passing through the helical quartz tube, the coarse quartz granules being of high purity and a diameter of 0.25-1.0 min.
All surfaces with which the water being purified comes into contact should be either quartz, gold or very pure stainless steel.
In another less expensive form the apparatus includes, connected in series: a first reactor including a bed of coarse quartz granules, a first filtration stage including a micro-filter, a second filtration stage including a micro-filter, a UV radiator to remove microbes including a quartz tube through which water to be purified passes and an ultraviolet light source to irradiate water passing through the quartz tube, a third filtration stage including an ultrafilter, a second reactor including a bed of gold, and an irradiation stage including a quartz tube through which water to be purified passes and a laser light source with a wavelength in the range of 200-300 nm to irradiate water passing through the quartz tube.
The invention also provides a method of purifying water including passing the water through the following steps in series:
removing microbes and photo-oxidizing chemicals in a helical quartz tube by irradiation of the water with ultraviolet light,
filtering out microbes in a fine filter and an ultra-fine filter,
exciting a bed of coarse quartz granules with heat from the ultraviolet light absorbed by the water so that the granules vibrate and destroy microbes, followed by sterilization of the water by exposure to a bed of noble metal,
filtering out microbes in a fine filter and an ultra-fine filter,
again removing microbes and photo-oxidizing chemicals in a helical quartz tube by irradiation of the water with ultraviolet light with coarse quartz granules in the tube,
exciting another bed of coarse quartz granules with heat from the ultraviolet light absorbed by the water so that the granules vibrate and destroy microbes, followed by sterilization of the water by exposure to a bed of noble metal,
exciting another bed of coarse quartz granules with heat from the ultraviolet light absorbed by the water so that the granules vibrate and destroy microbes,
filtering out microbes in a micro-filter
again removing microbes and photo-oxidizing chemicals in a helical quartz tube by irradiation of the water with ultraviolet light with coarse quartz granules in the tube,
filtering out microbes in an ultrafilter,
sterilizing the water by exposure to gold,
irradiation the water with laser light with a wavelength in the range of 200-300 nm,
whereby microbes in the water are killed and removed.
In a less expensive form the method includes passing the water through the following steps: removing microbes and photo-oxidizing chemicals in a helical quartz tube by irradiation of the water with ultraviolet light, exciting a bed of coarse quartz granules with heat from the ultraviolet light absorbed by the water so that the granules vibrate and destroy microbes, followed by sterilization of the water by exposure to a bed of noble metal, sterilizing the water by exposure to gold, and irradiation the water with laser light with a wavelength in the range of 200-300 nm, whereby microbes in the water are killed and removed.
Preferably, the method includes bottling the purified water in clean glass bottles while providing a blanket of ozone at the interface between the purified water and atmosphere as water is being filled into the bottles.
In another less expensive form, the method includes passing the water through the following steps in series: removing microbes and photo-oxidizing chemicals in a helical quartz tube by irradiation of the water with ultraviolet light, filtering out microbes in a fine filter and an ultra-fine filter, exciting a bed of coarse quartz granules with heat from the ultraviolet light absorbed by the water so that the granules vibrate and destroy microbes, followed by sterilization of the water by exposure to a bed of noble metal, filtering out microbes in a fine filter and an ultra-fine filter, whereby microbes in the water are killed and removed.
Preferably, the removing step includes passing air around the quartz tube, resulting in the formation of ozone, and bubbling the ozone through the water.
Typically, the first filtering step creates a back-pressure on the water in the removing step, and the water is heated in the removing step by the ultraviolet light source, resulting in oscillations in the water which are destructive to the microbes.
Desirably, the method includes a second removing step to remove microbes including passing the water through a quartz tube which contains coarse quartz granules of high purity and a diameter of 0.25-1.0 mm and irradiating the water with ultraviolet light, resulting in oscillations of the quartz granules in the water which are destructive to the microbes.
In another less expensive form the method includes passing the water through the following steps in series: passing the water through a bed of coarse quartz granules, filtering out microbes in a micro-filter, removing microbes and photo-oxidizing chemicals in a helical quartz tube by irradiation of the water with ultraviolet light with coarse quartz granules in the tube, filtering out microbes in an ultrafilter, sterilizing the water by exposure to gold, and irradiating the water with laser light with a wavelength in the range of 200-300 nm, whereby microbes in the water are killed and removed.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood by the reading of the detailed description of the preferred embodiment, along with a review of the drawings in which:
FIG. 1 is a block diagram of the various components used in a preferred embodiment, along with optional valve arrangements for less complete water treatment;
FIG. 2 is a sectional view through a UV radiator component used in the embodiment of FIG. 1;
FIG. 3 is a sectional view through a reactor cartridge according to the embodiment of FIG. 1;
FIG. 4 is an enlarged side view of a laser radiation component according to the embodiment of FIG. 1; and
FIG. 5 is a sectional view of the laser radiation component of FIG. 4 taken along lines 5--5 and looking in the direction of the arrows.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention provides a method and apparatus for treating what is conventionally described as potable water to make it of a high degree of purity. The infeed water is preferably from a conventional municipal water supply and has gone through the conventional municipal water supply treatments, which may include various filtering and sedimentation steps. The origin of the water may be any desired source, such as a lake, a river, melting ice, desalinized sea water or collected rain water.
As seen in FIG. 1, the apparatus according to a preferred embodiment includes a number of modules thorough which the water is put, becoming all the more pure as it goes further through the system. Various ones of the components can be isolated and used separately through suitable activation of valves 32, 34, or valves 28, 30 or valves 51, 53. Preferably, the water is routed through all the components shown in FIG. 1 to achieve the highest degree of purity. As will be appreciated, routing thorough fewer components achieves some purification, but not as much as through all.
The following description will describe a thorough treatment of the water, passing through all of the components. As can be appreciated from a review of FIG. 1, fewer components may be used, such as by suitable activation of the above-mentioned valves.
The water is first introduced to a UV radiator 12 shown more clearly in FIG. 2 as a sectional view. The water is infeed through quartz tubing 100 which is directed to pass around a plurality of ultraviolet lamps 102. The transparent quartz tubing 100, of course, permits the ultraviolet light to pass through it, thus irradiating the water passing thorough the tubing. The quartz of the tubing needs to be of a very high purity. Mirrors 108 and 110 are provided to redirect ultraviolet light back to the quartz tubing in order to provide radiation as intense as possible. Preferably, the ultraviolet radiation is in the spectrum range of 180-300 nanometers and most preferably 254 nanometers. Also, preferably the UV lamps 102 are elongated and the quartz tubing spirals around the UV lamps in a helical fashion in order to maximize the period of time of the exposure of water passing through the quartz tubing to the ultraviolet light.
As an alternative, the water could be passed through straight tubes like tubes 102 with the ultraviolet light being emitted by a spirally wound tube like the tube 100. An arrow 104 indicates an air infeed path which is to provide cooling for the apparatus, under the influence of fan 106. The passage of the air through the intense ultraviolet light will cause the generation of ozone, which can be passed through the water to aid in purification. This is not shown in the drawings but may be done upstream in the municipal water system, or downstream of the UV radiator 12. From the UV radiator 12, the water is directed to a fine filter 14 and an ultra-fine filter 16.
After the ultra-fine filter 16, the water is passed through a reactor made up of stages 18 and 20. The lower portion 18 of the reactor is filled with coarse quartz granules, and the upper portion 20 is filled with noble metal balls. The balls are all of one noble metal, but may be any noble metal, including silver, gold, platinum, palladium, ruthenium, rhodium, iridium, and osmium. A preferred noble metal is silver. Preferably, the balls are provided with a lot of holes, providing a large surface area for intimate contact between the water and the noble metal. This provides a catalyst-like structure to maximum the effective area of the noble metal exposed to the water.
The two reactor bed stages 18 and 20 can be seen disposed in a canister arrangement in FIG. 3. The canister arrangement can be used for the various reactors shown in the drawing FIG. 1.
The canister 126 making up the reactor housing 120 mounts to a support 128 into which the water is introduced through an inlet 122. The inlet 122 leads to the bottom of the chamber 18 in which the quartz granules are disposed. Above the quartz granules 18 are the noble metal balls 20. From the top of the noble metal ball bed 20, the water exits through an exit 124. The provision of these components in a canister arrangement of this sort permits the cleaning or replacement of the quartz and/or noble metal balls, should that ever become necessary.
While the UV radiator itself is believed to kill perhaps some 20% of the microbes passing it thorough photo oxidation of the chemicals and the destruction of bacteria and virus, it also cooperates with the filter components 14 and 16. Pressure is created in the UV radiator by resistance from the filters and by expansion of the water from the heating inherent in the ultraviolet radiation. This can cause localized killing of the viruses and bacteria.
Furthermore, the downstream quartz granules in reactor 18 are provided in various sizes and purities to that the heat and pressure cause them to oscillate. This causes the emission of radiation that further destroys some viruses by penetrating membranes of the viruses.
The noble metal, particularly silver, in the reactor bed 20 has the property of a sterilizer. As the energized water from the quartz enters the silver bed, electrons in the silver travel faster and make additional radiation which can cause further viral destruction.
Downstream of the reactor beds 18 and 20 are further filter stages 22 and 24. The filter 22 is provided as a coarse filter with the filter 24 as a fine filter.
The water then passes into another UV radiator 26 which is much like the UV radiator 12, except that: the quartz tubing 100 is itself filled with quartz granules, so that the water passing through the tubing 100 of the UV radiator 26 is again in intimate contact with quartz granules. The ultraviolet light entering the tubing 100 of the UV radiator 26 causes the quartz granules to pulsate, to physically kill viruses and bacteria. The shapes of the granules of the quartz are not critical, but the preferably have a size range of 0.25 to 1.0 mm in diameter. Downstream of the UV radiator 26, the water passes through additional reactor bed 36 containing a noble metal, like the noble metal of the reactor bed 20 and into reactor bed 38, which contains quartz granules. From there, the water passes through a reactor bed 40 again having the noble metal and then into a reactor bed 42 having quartz granules. Next, the water is directed to a reactor 44 filled with only the quartz granules. Downstream of the reactor 44, the water passes thorough two microfiltration stages 48 and 50.
Downstream of the filter 50, the water passed through another UV radiator 52 identical in virtually all respects to the UV radiator 12.
The output of UV radiator 52 is then passed through ultra filter 54 and through a further reactor 56 filled with gold balls again having a catalyst-style surface. The gold "polishes" the water, providing more virus killing ability. The water passing from the reactor 56 is then passed through a laser irradiation component 58. This component can be better seen in FIGS. 4 and 5. The laser 142 preferably emits a wide beam of laser light of a wavelength in the range of 200-300 nanometers to fully cover the quartz tube 140 through which the water passes. A mirror 144 may be provided to further irradiate the water in the tube 140. An air flow 146 may again be provided for cooling the quartz tube. The resulting ozonated air may be passed through one of the earlier pretreatment stages, as discussed above. The water output of the laser irradiation component 58 is then applied to a storage tank 60.
A bottling preparation facility 62 may be provided in which the bottles that are to be stored and shipped are irradiated with ultraviolet light and ozone is supplied in place of air, to keep out contaminants. Preferably the bottles are quartz glass in order to prevent the leaching of contaminants into the water. Alternatively, a silver-lined, plastic bottle could be used or other leach-free glass. The water is supplied from the storage tank 60 for filling in the bottles from the supply 62 under a constant ultraviolet illumination and/or ozone in order to prevent recontamination.
The piping connecting the various components must be of character so as not to introduce contaminants such as by dissolving into the water. Thus, the piping and the storage tank 60 should be quartz, gold-plated or a very high grade of stainless steel. Also, it is desirable to fill the ullage of the tank 60 with ozone, such as the ozone generated by the laser 58.
The operation of the apparatus is straight-forward. The UV radiator 12 receives the infeed from municipal water supply and then passes the feed thorough the filter stages 14 and 16. From there it is passed through the reactors 18 and 20 and through the filters 22 and 24. Then, depending on the settings of the valves 28 and 30, the water may pass to UV radiator 26, reactors 36, 38, 40, 42 and 44 and filter stages 48 and 50. A lesser degree of purification can be obtained by closing valve 34 and opening valve 32 and directing the water from the municipal water supply directly to the reactor 44, bypassing the earlier elements.
Similarly, if the valve 28 has been closed and the valve 30 has been opened, the water will have bypassed the components from UV radiator 26 to the filter 50 and applied directly to UV radiator 52, if valve 53 is opened. If, instead, valve 53 is closed and valve 51 is open, the water would immediately go to storage 60. With the valve 53 open, the water passes through UV radiator 52, ultra filter 54 and gold bed 56 before passing to the laser irradiation component 58 and to storage 60.
When filters are part of the system, they are desirably changed occasionally.
While the use of the noble metals and gold may entail a high expenditure to establish the apparatus in the invention, the operating costs are very low.
Those of ordinary skill in the art will appreciate that various modifications can be made to the apparatus as specifically and still fall within the scope of the invention.
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An apparatus for purifying water includes:
a plurality of UV radiators which include a helical quartz tube through which water to be purified passes and an ultraviolet light source to irradiate water passing through the helical quartz tube to remove microbes,
a plurality of filtration stages including fine, ultra-fine and micro filters,
a reactor including a bed of gold, and
an irradiation stage including a quartz tube through which water to be purified passes and a laser light source with a wavelength in the range of 200-300 nm to irradiate water passing through the quartz tube,
whereby microbes in the water passing through the apparatus are killed and removed.
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BACKGROUND OF THE INVENTION
This invention relates to roadway surface reconditioning apparatus and more specifically to a machine for scarifying and in-place recycling of asphalt or like bituminous road surfaces.
The term "scarifier" is used herein to denote a machine that travels slowly along a roadway while heating the existing asphalt to a relatively high temperature. It then loosens the hot asphalt with a scarifying assembly to a depth of typically about an inch. Finally it smooths down the loosened hot material to form a reconditioned and resurfaced roadway. In some cases a liquid rejuvenator and/or new asphalt can be added before the smoothing stage. The scarifier is followed by a roller for further compressing the material while it is still relatively hot.
A typical prior scarifier is disclosed in U.S. Pat. No. 3,989,401 issued Nov. 2, 1976 to F. F. Moench.
A critical part of such a machine is a heater assembly for applying heat to the old roadway surface. It is desirable to apply as much heat as possible to the asphalt, and to do so as quickly as possible, because the amount of heat that can be transferred to the asphalt per unit time will determine how fast the machine can travel along the road and hence how many miles of road one machine can treat in a day. The efficiency of heat transfer will also determine the depth to which the asphalt can be heated to the extent required to enable it to be loosened by the scarifying teeth. For example, existing machines can typically travel at about 15 feet per minute, based on treating at the most the top one inch of asphalt. Such operation would require a maximum heater output of about 60,000 BTU per square foot per hour.
Many past attempts to increase the amount of heat transferred to the roadway surface have resulted in either setting fire to the asphalt or burning it to such an extent that it could no longer be reused without extensive reconditioning. Machines of this type have also been blamed for starting fires among shrubs and other vegetation along the side of the road, due to uncontrolled excessive heat.
Another problem that has been experienced in these machines in the past is adaption of the scarifying assembly to variations in roadway surface conditions, especially irregular profiles and widths.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a heater assembly for use in such a machine, such assembly being capable of transferring heat to the roadway material more effectively and efficiently than has been possible with past machines. Such an improved heater assembly is expected to permit a heat transfer of as high as 150,000 BTU per square foot per hour when needed, with a typical daily operating transfer rate of the order of 80 to 100,000 BTU per square foot per hour, and moreover to achieve these rates without burning the material or otherwise seriously deteriorating its quality and without subjecting the surroundings to the risk of brush fires or the like. With such a high heat transfer rate, it is possible to operate the machine at a speed of up to about 25 feet per minute and/or to increase the scarifying depth to as much as about 11/2 inches with a consistent minimum of an inch, even at the edges of the machine, which is a location at which it is often difficult to achieve full performance.
Another object of the present invention is to provide an improved scarifying assembly for loosening the roadway surface after it has been softened by heating and prior to its being resmoothed, and in particular to provide a scarifying assembly that is versatile in enabling the operator to adapt it to variations in roadway conditions while scarifying to the full depth of the heated asphalt.
DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 shows a side view of a scarifier embodying the present invention;
FIG. 2 is a plan view of FIG. 1;
FIG. 3 is a schematic diagram of the fuel supply to the heater assembly;
FIG. 4 is an underside view of a heater unit, partly broken away;
FIG. 5 is a sectional view on the line V--V in FIG. 4;
FIG. 6 is a partly broken away side view taken on the line VI--VI in FIG. 4;
FIG. 7 is a fragment of FIG. 1 showing details on a much enlarged scale;
FIG. 8 is a side view of a portion of FIG. 1 showing a modificiation;
FIG. 9 is a plan view of FIG. 8;
FIG. 10 is a plan view of a scarifying portion of FIG. 1 showing on an enlarged scale another modification; and
FIG. 11 is a side view of FIG. 10.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The machine shown in FIGS. 1 and 2 is a vehicle having a main frame formed by a pair of horizontal beams 10 mounted on front wheels 11 and rear wheels 12 driven from an engine unit 13. At the extreme rear there is a conventional screed assembly 14 for smoothing the material that has been broken up by scarifying teeth 15 after heating by a heater assembly 16.
The heater assembly 16 consists of twenty one heater units 17 arranged in three forward and intermediate banks 18a, 18b and 18c of six units each and a rearmost bank 18d of three units. In each bank, three units 17 are arranged end to end to form rows extending across the machine. In the forward and intermediate banks there are two such rows, one in front of the other, and in the rearmost bank there is only one such row. Heat deflectors 19 are provided between adjacent banks 18a to d. As explained more fully below these heat deflectors 19 serve to reflect or reradiate heat down towards the roadway.
The heater banks are secured to and supported by horizontal beams 20 and can be raised and lowered as an assembly by the operator by means of hydraulic cylinders 21 mounted on the main beams 10 and acting through linkage systems 22 and transverse bars 23 pivotally mounted on the main beams 10. By operating one cylinder 21 more than the other this assembly can be tilted forward or backwards to vary the distance between the ground and either the forward or rearward heater banks.
As shown in FIG. 7, each heater unit 17 is secured to the beams 20 by means of pairs of bolts 90 (one behind the other in FIG. 7) which are welded to the heater unit 17 at 90' and extend upwardly to pass through a transverse bar 91 extending across the top of the beam 20. This arrangement is secured by nuts 92. Each heat deflector 19 preferably consists of a steel back plate 94 to which a refractory panel 95 is adhered (although a plain steel sheet can be used). Along each edge, bolts having heads 96 embedded in the refractory panel 95 serve with nuts 97 to secure the plate 94 to steel angle beams 93 welded to the sides of the heater units 17.
This arrangement permits easy variation of the spacing between the heater banks in the direction of travel. The nuts 92 are loosened, and the nuts 97 and the deflectors 19 are removed. One or more of the heater banks is then moved along the beams 20 to a desired new location and the nuts 92 retightened. New deflectors 19 dimensioned to fit the new spacing between the heater banks are then secured in place by the nuts 97.
Each of the heater units 17, shown individually in FIGS. 4 to 6, consists of a heater of the so-called luminous wall type, consisting of a steel frame 30 supporting a series of porous firebricks 31. These bricks 31 are so designed that a gaseous fuel consisting of a mixture of propane and air introduced into a hollow rear space 42 of the frame 30 through a pipe 80 can flow through the bricks 31 and burn at or adjacent the surfaces thereof to provide a large area radiant heater. Around the perimeter of the frame 30 there are raised porous edge members 32 that serve to ensure a minimum spacing 33 between the heater surface 34 and a roadway surface. All the edge members 32 are connected to an air supply by pipes 81 and hence serve to discharge downwardly a curtain of air around the entire unit 17. This arrangement tends to minimise the risk of combustible fuel or flames escaping sideways from the unit and presenting a threat to persons or objects in the vicinity. It also cools and hence protects the steel frame.
Expansion material 35, preferably in the form of a composition of the aluminum silicate type, such as that known under the trade mark Kaowool, is located around the entire assembly of twenty five bricks 31 and between and around the individual bricks 31 in such a way that every brick has this material extending along at least two adjacent sides thereof. In other words, each brick has freedom to expand and contract in both directions with temperature changes. At those locations where the bricks abut each other without interposed expansion material 35 they are joined by mortar 36. Each brick 31 is securely connected to the frame 30 by means of a centrally located bolt 37 (the centre brick has two such bolts arranged one on each side of the pipe 80) that extends through the frame 30 and through four layers of wire mesh 38 to engage nuts 39 firmly mounted in the centre of each brick by mortar 40. The surface of the frame 30 facing the wire mesh 38 and the bricks 31 is in the form of a perforated plate 41 through which the fuel mixture can flow to reach the bricks. Finally, the bricks are held in place by transverse rods 83 two of which pass horizontally through each brick and are tightly fastened by nuts on the outer sides of the frame 30.
It will now be convenient to refer to FIG. 3 which shows the air-fuel system schematically. This system consists of a propane tank 50 from which liquid and gaseous propane is drawn off in the usual way through piping 51 and valves 52 to a bank of three vaporizers 53 arranged in parallel. At valves 54 on the downstream side of the vaporizers 53 there will be gaseous propane at a pressure of about 100 pounds per square inch. This gas passes through a pair of parallel-arranged, gas pressure regulators 55 where its pressure is reduced to about 5 pounds per square inch, as indicated by a gauge 56. It then passes through a safety shut-off valve 57, the function of which will be described below, to gas portions 58a of a pair of ratio valves 58.
The air system begins at a blower 60 driven by a motor 61 (FIGS. 1 and 2) that supplies air in pipe 62 to air portions 58b of the ratio valves 58. These known valves can be manually operated to control the exact amount of heat emitted by either of the two portions (shown at the top and bottom respectively of FIG. 3) into which the heater assembly is divided. Regardless of the position, i.e. degree of opening, of each valve 58, the ratio between the amount of propane gas and the amount of air passed through the respective valve portions 58a and 58b always remains constant. Of course, this ratio can be changed as desired and will initially be set by the operator. However, once so set it will be maintained automatically, regardless of the degree of opening of each of these valves. These valves 58 can alter the total heat from 30,000 B.T.U. per square foot per hour to 150,000 B.T.U. per square foot per hour, while maintaining uniform application of that heat.
The upper pair of valve portions 58a and 58b seen in FIG. 3 supply gas and air through respective pipes 63 and 64 to a first series of gas-air proportional mixers 65. One such mixer is mounted on top of each heater unit 17 of the nine such units of banks 18c and 18d (represented by the four upper units 17 shown in FIG. 3). Similar pipes 66 and 67 respectively supply gas and air from the lower pair of valve portions 58a and 58b to a second series of similar gas-air proportional mixers 65 mounted on top of respective ones of the twelve heater units 17 of the front banks 18a and 18b (represented by the four lower units 17 shown in FIG. 3). The supply lines 63 and 66 pass gas to the mixers 65 through individual, manually operated, control valves 82 and shut-off valves 68. Each valve 68 also includes a second, transverse passage 69, the respective passages 69 being arranged in series in a line 70 that extends from the gas supply through a manual valve 71 and ends at a control mechanism 72 controlling the safety valve 57. Initially, before any of the heater units 17 can be started up, all the valves 68 must be closed in respect of the lines 63 and 66. When they are all thus closed, their passages 69 will all be open, and hence the line 70 will be open, allowing gas pressure to pass through the valve 71 and the line 70 to the gas pressure side 72a of the control mechanism 72.
Assuming that there is simultaneously air pressure from the line 62 on the air pressure side 72b of the control mechanism 72, this mechanism is enabled for manual operation by a lever 72c to open the safety valve 57 and admit gas to the ratio valves 58 and hence eventually to the heater units. So long as gas pressure is maintained between the valves 57 and 58 and there is air pressure in the line 62, the control mechanism 72 will remain in the open condition without reliance on pressure from the line 70. Thus, as part of the start-up procedure, the valve 71 can now be closed manually and each of the valves 68 can be opened manually with the gas-air mixture that now flows in lines 80 and appears at the respective heater units 17 being ignited. In practice, the valves 68 will preferably be ganged in groups of three across the machine. If, at any time while the machine is operating, there should be a loss of gas or air pressure on either side of the control mechanism 72, such loss will automatically shut off the safety valve 57 which cannot then be reopened manually until both the gas and air pressures have been restored. In the case of the gas pressure, such restoration must be achieved by use of the valve 71 and line 70 which necessitates first opening all the passages 69, i.e. closing all the valves 68 to shut down the entire heater assembly. Hence, for reasons of safety, no heater unit can be relit until all of them have been shut down and the two pressures (gas and air) reestablished.
The manually operable valves 82 enable the operator to adjust the amount of heat being given off by one pair of heaters 17 relative to each other pair. In this way the apparatus enables the operator to compensate for any temperature gradient that might arise in the transverse direction of the machine as a result, for example, of an uneven roadway surface, an off-level condition of the machine or different edge spacings (heights) from the road surface. These valves also allow the operator to shut off a complete row of heaters from front to back, being either the left, center or right row, so that with suitable adjustments to the scarifying and screed assemblies, the machine can quickly be converted to scarify a variety of widths of roadway.
While an important feature of the overall assembly that constitutes the present invention is the use of the luminous wall type of heater, it should be explained that this type of heater is already known per se for use in radiant heating applications, for example in U.S. Pat. Nos. 2,828,813 issued Apr. 1, 1958 to A. F. Holden; 3,008,513 issued Nov. 14, 1961 to A. F. Holden; 3,076,605 issued Feb. 5, 1963 to A. F. Holden and 3,224,431 issued Dec. 21, 1965 to A. F. Holden, and has been disclosed for use in a scarifier in U.S. Pat. No. 3,970,404 issued July 20, 1976 to A. W. Benedetti.
FIGS. 8 and 9 show an optional additional feature in the form of a preheater assembly 99 mounted on the front of the vehicle, i.e. forward of the front wheels 11. This assembly 99 consists of a frame 100 slidably mounted on the vehicle for vertical movement under the control of chains 101 operated by hydraulic cylinders 102. The frame 100 supports arms 105 on hinges 103. The arms 105 carry a fifth bank 18e of heater units 17 similar to the heater bank 18d. Further vertical and tilting adjustment of the orientation of the heater bank 18e is achieved through hydraulic cylinder 104. Gas and air are supplied to the assembly 99 through tubing 106 (only partially shown) in the same manner as to the other heater banks.
The assembly 99 will be stored in a vertical orientation (by retraction of the cylinder 104). The cylinders 102 and 104 will be operator controlled and when the assembly is in use these cylinders will adjust the orientation of the heater bank 18e and the distance between its heating surfaces and the roadway surface.
The present inventors have found that the improved results postulated above can be achieved with the apparatus disclosed herein, and that important aspects of this apparatus for obtaining these results are use of the luminous wall type of heaters including not only a radiating surface of porous fire bricks 31 supplied with air/gas mixture but also porous side walls 32 for directing curtains of air downwardly to inhibit sideways escape of heat from the region beneath each heater, and the assembling of the heaters into at least two banks of heaters (and preferably as many as the four such banks 18a to 18d plus the addition of the preheater assembly 18e, when required), these banks being spaced apart in the travelling direction and bridged by the heat deflectors 19 and such spacing being adjustable in length. In addition to reducing the heat loss upwardly between the heater banks, these deflectors either reflect or reradiate heat back down to the portion of the roadway surface that is momentarily located between the heater banks. This arrangement achieves an important heat soak stage. Each heater bank projects very intense heat down against the roadway surface beneath it. This heat needs some time to penetrate to the desired depth. If the intense heat were continued uninterruptedly, i.e. if there were no spacing between the heater banks in the travelling direction, the upper surface of the roadway could be damaged by reaching too high a temperature (or the rate of application of heat would have to be reduced, which would defeat the basic objective). Hence the spacing between heater banks is essential in order to give the road surface a soaking period for the heat to penetrate. On the other hand, it is desirable to minimise the escape of heat during this soaking period. This is the important function that the heat deflectors 19 play.
The freedom provided by the present arrangement to vary the spacing between a pair of heater banks and hence the size of the heat deflectors 19 bridging such pair of banks together with the other variables already discussed, such as varying the amount of fuel to each heater and the height of respective heaters above the roadway, combine to enable choice of an optimum relationship between the magnitude and duration of each heat application by a heater bank and the magnitude and duration of each heat soak period when the roadway surface is directly receiving only the deflected heat from the deflectors 19, such optimum relationship depending on the asphalt type, roadway condition, the depth of scarifying required and seasonal variations of ambient temperature.
As indicated above, the rate of heat application can be adjusted by changing the height of the heater banks above the roadway surface. With very cold seasonal temperatures, the front of the heater assembly is lowered close to the roadway surface to give maximum heat penetration into the initially very cold asphalt. On the other hand, if the machine encounters a roadway with extensive prior crack filling, the rear of the heater assembly can be raised further above the roadway surface, since the crack-sealing material would otherwise tend to burn before the asphalt is fully heated.
The preheater assembly 99 is normally used when cold weather conditions or certain asphalt types that are more difficult to heat are encountered.
The use of heat shields in a road maintenance machine is known from U.S. Pat. No. 3,997,276 issued Dec. 14, 1976 to J. A. Jackson, Sr.
As shown in FIGS. 10 and 11, the apparatus may include a modified scarifying assembly 110 consisting of a forward portion 111 and a rear portion 112. The forward portion 111 has transverse bars 113 and 114 mounting staggered rows of conventional scarifying teeth 15. Each bar 113, 114 is mounted by means of straight leaf springs 115 on an upper cross bar 116 forming part of a main frame 117. In practice this frame (and its associated parts) will be divided in the transverse direction into at least two and preferably three separate sections. There will thus be three separate frames 117a, 117b and 117c, each of which at its front edge swivels about pins 118 carried by a forward frame 119 which itself can pivot on an axis 120 about the vehicle frame members 10. Pivoting movement of the forward frame 119 is controlled by hydraulic cylinders 121, and pivoting movement of the associated main frames 117a, 117b and 117c about the front frame 119 is controlled by hydraulic cylinders 122. As a result, the operator can control both the scarifying depth and the angle of attack of the teeth 15 of the forward scarifying portion 111 and he can adjust these requirements differently in sections across the machine.
The rear scarifying portion 112 is also divided transversely into a plurality of sections, and in this case the preferred number is six. Each such section has a transverse bar 123 mounting a row of conventional scarifying teeth 15. The bar 123 is mounted on lower ends of curved leaf springs 124, the upper end of each such leaf spring 124 being connected to one arm of a bell-crank member 125 pivoted about a pin 126 to a main cross beam 127. The other arm of each bell-crank member 125 is secured to one end of a coil spring 128 mounted at its other end to a casing 129 projecting forwardly from the beam 127 and also serving to partially shield the spring. Each section of the beam 127 carries an arm 130 to enable a hydraulic cylinder 131 to rotate such beam section about a pivotal axis 132 defined by arms 133 secured to the main frame of the vehicle. The operator can adjust the scarifying depth of the teeth 15 of each section of the rear scarifying portion 112 by means of respective cylinders 131. Also, each section can flex upwardly if excessive resistance is encountered by any of its teeth, such flexure being principally provided by stressing the coil springs 128 in tension.
The rear scarifying portion 112 is preferably divided into a larger number of transversely separate sections, e.g. 6, than the forward scarifying portion 111, e.g. 3 (although these numbers can be varied to suit different requirements), because the rear portion 112 is the one that principally determines the overall depth of scarifying. If the machine encounters a roadway surface with a drastically varying surface profile, it requires the versatility to adapt to such profile while still performing reasonably uniform scarification.
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In a roadway surface reconditioning apparatus, for example, a scarifier for use with an asphalt or like bituminous roadway surface, a number of heaters of the luminous wall type are employed to direct large quantities of radiant heat downwardly towards the surface for softening it while travelling along the roadway. These heaters consist basically of porous fire bricks through which an air/propane mixture passes and on the surface of which it burns. Each heater also has porous side walls that project closer to the roadway surface than the main bricks and are supplied with air for forming a downward curtain of air to inhibit sideways escape of heat from the region beneath the heater. The heaters are assembled in banks that are spaced apart from each other in the direction of travel. This spacing can be adjusted. Each pair of adjacent banks is bridged by heat deflectors that help to provide heat soak areas between the heater banks. The apparatus also includes a novel scarifying assembly with increased adjustability of the scarifying depth of the teeth.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 13/370,674, filed Feb. 10, 2012, issuing as U.S. Pat. No. 8,505,525 on Aug. 13, 2013, which is a continuation of U.S. patent application Ser. No. 12/271,402, filed Nov. 14, 2008, which issued as U.S. Pat. No. 8,113,189 on Feb. 14, 2012, which is a continuation of U.S. patent application Ser. No. 11/352,639, filed Feb. 13, 2006, which issued as U.S. Pat. No. 7,451,755 on Nov. 18, 2008, which is a continuation-in-part of U.S. patent application Ser. No. 11/183,548, filed Jul. 18, 2005, now abandoned, which claims the benefit of U.S. Provisional Patent Application Nos. 60/588,912, filed Jul. 16, 2004 and 60/654,262, filed Feb. 18, 2005 respectively, and also claims the benefit of U.S. Provisional Patent Application Nos. 60/652,157, filed Feb. 11, 2005 and 60/654,120, filed Feb. 18, 2005 respectively, all of which are incorporated by reference as if fully set forth herein.
BACKGROUND
This invention relates generally to the construction of compressed gas guns and more particularly to the guns designed to propel a liquid containing frangible projectile, otherwise known as a “paintball.” As used herein, the term “compressed gas” refers to any mean known in the art for providing a fluid for firing a projectile from a compressed gas gun, such as a CO2 tank, a nitrous tank, or any other means supplying gas under pressure. Older existing compressed gas guns generally use a mechanical sear interface to link the trigger mechanism to the hammer or firing pin mechanism. In these guns, a trigger pull depresses the sear mechanism which allows the hammer, under spring or pneumatic pressure, to be driven forward and actuate a valve that releases compressed gas through a port in the bolt, which propels a projectile from the barrel.
This design, however, has many problems, including increased maintenance, damage after repeated cycles, and a higher amount of force is required to drive the hammer mechanism backwards to be seated on the sear. Also, because the sear and resulting hammer must be made of extremely hard materials, the gun is heavy. Such weight is a disadvantage in paintball, where a player's agility works to his advantage.
To overcome the problems of a mechanical sear, other solutions have been developed. One solution uses a pneumatic cylinder, which uses spring or pneumatic pressure on alternating sides of a piston to first hold a hammer in the rearward position and then drive it forward to actuate a valve holding the compressed gas that is used to fire the projectile. Although the use of a pneumatic cylinder has its advantages, it requires the use of a stacked bore, where the pneumatic cylinder in the lower bore and is linked to the bolt in the upper bore through a mechanical linkage. It also requires increased gas use, as an independent pneumatic circuit must be used to move the piston backwards and forwards. A further disadvantage is that adjusting this pneumatic circuit can be difficult, because the same pressure of gas is used on both sides of the piston and there is no compensation for adjusting the amount of recock gas, used to drive it backwards, and the amount of velocity gas, which is the amount of force used to drive it forward and strike the valve. This results in erratic velocities, inconsistencies, and shoot-down. In addition, this technology often results in slower cycling times, as three independent operations must take place. First, the piston must be cocked. Second, the piston must be driven forward. Third, a valve is opened to allow compressed gas to enter a port in the bolt and fire a projectile. Clearly, the above design leaves room for improvement.
Single-bore designs have been developed which place the cylinder and piston assembly in the top bore, usually behind the bolt. This reduces the height of the compressed gas gun, but still requires that a separate circuit of gas be used to drive the piston in alternating directions, which then actuates a valve to release compressed gas, which drives the bolt forward to launch a paintball. These are generally known as spool valve designs. See, for instance, U.S. Pat. Nos. 5,613,483 and 5,494,024.
Existing spool valve designs have drawbacks as well. Coordinating the movements of the two separate pistons to work in conjunction with one another requires very precise gas pressures, port orifices, and timing in order to make the gun fire a projectile. In the rugged conditions of compressed gas gun use, these precise parameters are often not possible. In addition, adjusting the velocity of a compressed gas gun becomes very difficult, because varying the gas pressure that launches a paintball in turn varies the pressure in the pneumatic cylinder, which causes erratic cycling.
What is needed is a compressed gas gun design that eliminates the need for a separate cylinder and piston assembly and uses a pneumatic sear instead of a pneumatic double-acting cylinder to hold the firing mechanism in place prior to firing a projectile. This allows the gun to be very lightweight and compact, and simplifies adjusting the recock gas used to cock the bolt and the gas used to fire the projectile. A further need exists for an easily removable inline cylinder that can be removed, preferably without using tools, so that the marker can be field-stripped and maintained.
SUMMARY
The current invention addresses these needs. The main advantage is that the inventive inline cylinder includes a gas governor that reduces gas flow from a compressed gas source to a valve area when the bolt is in a firing position; this increases efficiency in the marker because only the required air is used to fire the paintball. This particular design operates independent of the valve pin, which increases cycle speed and enables the governor to open and close at the optimum time in the firing cycle. Further, when the bolt/piston is recocking, the gap between the valve pin and governor valve pin enables low pressure gas driving the piston to start pressurizing the cylinder and driving the piston rearwards without resistance from the high pressure gas.
It allows a user to remove the inline cylinder without the use of tools, and gives the user a convenient carrying handle for holding the paintball marker, which is commonly called a “snatch grip.”
Further, the invention uses a safety mechanism that prevents the inline from being removed while the marker is pressurized without the safety, such removal would result in the inline cylinder being driven backwards out of the marker.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects of the invention will be more readily apparent upon reading the following description of embodiments of the invention and upon reference to the accompanying drawings wherein:
FIG. 1 is a side view of a compressed gas gun utilizing a variable pneumatic sear in the firing position.
FIG. 2 is a side view of a compressed gas gun utilizing a variable pneumatic sear in the loading position.
FIG. 3 is an expanded view of the variable pneumatic sear in the loading position.
FIG. 4 is an expanded view of the variable pneumatic sear in the launching position.
FIG. 5 is an expanded isometric view of the switches located within the recess.
FIGS. 6 and 6A are cross-sections of an alternate embodiment showing an inline cylinder in the loading position.
FIGS. 7 and 7A are cross-sections of an alternate embodiment showing an inline cylinder in the firing position.
FIG. 8 is a cross section of the rear end of the marker having the inline cylinder of FIG. 6 .
FIG. 9 is a cross section of the rear end of the marker having the inline cylinder of FIG. 6 .
FIG. 10 is a cross section of the rear end of the marker having the inline cylinder of FIG. 6 .
FIG. 11 is an elevation of the rear end of the marker having the inline cylinder of FIG. 6 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1-5 illustrate of a compressed gas gun incorporating a pneumatic sear. Referring to FIGS. 1 and 2 , a paintball gun generally comprises a main body 3 , a grip portion 45 , a trigger 24 , a feed tube 6 , and a barrel 10 . These components are generally constructed out of metal, plastic, or a suitable substance that provides the desired rigidity of these components. Main body 3 generally is connected to a supply of projectiles by feed tube 6 as understood by those skilled in the art. Main body 3 is also connected to grip portion 45 , which houses the trigger 24 , battery 64 and circuit board 63 . The trigger 24 is operated by manual depression, which actuates micro-switch 86 directly behind trigger 24 to send an electrical signal to circuit board 63 to initiate the firing or launching sequence. Barrel 10 is also connected to body 3 , preferably directly in front of feed tube 6 , to allow a projectile to be fired from the gun.
Hereinafter, the term forward shall indicate being towards the direction of the barrel 10 and rearward shall indicate the direction away from the barrel 10 and towards the rear of main body 3 . Preferably forward of the grip portion 45 , and also attached to main body 3 , the regulator mount 2 houses both the low-pressure regulator 21 and the high-pressure regulator 50 . Compressed gas is fed from preferably a compressed gas tank into the input port 49 on high-pressure regulator 50 to be directed to tube 7 to launch a projectile and to be directed to low pressure regulator 21 to cock the bolt tip 38 for loading. Both regulators 21 , 50 are constructed from principles generally known to those skilled in the art, and have adjustable means for regulating compressed gas pressure.
Referring more particularly to FIGS. 3 and 4 , housed within main body 3 is the firing mechanism of the gun. The firing mechanism preferably comprises a bolt tip 38 , which is preferably constructed out of delrin or metal and is connected to piston 32 , housed in cylinder body 31 . Piston 32 is also constructed out of delrin or metal, and is connected to valve pin 33 , housed on the interior of piston 32 . In the loading position, valve pin 33 is forced rearward by compressed gas at a low pressure (described in more detail below) and seal 70 (located on a rearward portion 33 a of the valve pin 33 ) is pushed against the lip 75 of valve housing tip 35 , holding high-pressure compressed gas A on the rearward face 33 b of valve pin 33 and preventing the flow or high pressure gas through bolt tip 38 . All seals, including o-ring 70 are constructed out of urethane, plastic, rubber, silicone, BUNA, TEFLON, or any other substance that effectively prevents gas leakage beyond the surface of the seal. Valve housing tip 35 is integrally connected to valve housing 34 , which prevents leakage of high-pressure compressed gas around the valve housing 34 . Seals 102 also prevent leakage of high-pressure gas and are placed at connecting section of the various components. Cylinder 31 surrounds valve housing 34 and provides sealed housing for piston 32 , which contains a first surface 72 for low pressure gas B to flow into to drive piston 32 rearward and seal valve pin 33 against tip 35 . Valve housing 34 preferably contains an interior chamber 36 for storing compressed gas to be used to fire a projectile from the gun.
The variable pneumatic sear 29 of the compressed gas gun of the present invention preferably consists of a control valve 30 , a piston 32 , residing in preferably sealed cylinder housing 31 as shown in FIG. 1 . Control valve 30 directs low pressure compressed gas from low pressure regulator 21 through manifold 41 to the cylinder housing 31 , allowing gas to contact first surface of piston 32 , driving the piston 32 rearward to seat the valve pin 33 when de-actuated, which is considered the loading position. The low pressure compressed gas is able to drive the piston 32 rearward against high-pressure gas pressure on valve pin 33 because the surface area of first surface 72 of piston 32 is larger than that of the surface of valve pin 33 . Control valve 30 preferably consists of a normally open three-way valve. When actuated, a normally open valve will close its primary port and exhaust gas from the primary port, thereby releasing pressure from the first surface of piston 32 , through a port 42 drilled into manifold 41 . This allows high pressure compressed gas, pushing against the smaller surface area of valve pin 33 , to drive valve pin 33 forward and break the seal by o-ring 70 to release the stored gas from valve housing 34 . Compressed gas then flows around valve pin 33 , through ports 32 a in piston 32 , and out through bolt tip 38 to launch a projectile from the barrel 10 .
Control valve 30 is preferably controlled by an electrical signal sent from circuit board 63 . The electronic control circuit consists of on/off switch 87 , power source 64 , circuit board 63 , and micro-switch 86 . When the gun is turned on by on/off switch 87 , the electronic control circuit is enabled. For convenience, the on/off switch 87 (and an optional additional switches, such as that for adjacent anti-chop eye that prevents the bolt's advance when a paintball 100 is not seated within the breech) is located on the rear of the marker, within a recess 88 shielded on its sides by protective walls 89 . This location protects the switch 87 from inadvertent activation during play. The switch 87 is preferably illuminated by LEDs.
When actuating switch 86 by manually depressing trigger 24 , an electrical signal is sent by circuit board 63 to the control valve 30 to actuate and close the primary port, thereby releasing valve pin 33 and launching a projectile. Once the momentary pulse to the control valve 30 is stopped by circuit board 63 , the electronic circuit is reset to wait for another signal from switch 86 and the gun will load its next projectile. In this manner, the electrical control circuit controls a firing operation of the compressed gas gun.
A description of the gun's operation is now illustrated. The function of the pneumatic sear is best illustrated with reference to FIGS. 3 and 4 , which depict the movements of piston 32 more clearly. Compressed gas enters the high-pressure regulator 50 through the input port 49 . The high-pressure regulator is generally known in the art and regulates the compressed gas to about 200-300 p.s.i. These parameters may be changed and adjusted using adjustment screw 51 , which is externally accessible to a user for adjustment of the gas pressure in the high-pressure regulator. This high-pressure gas is used to actuate the firing valve and launch a projectile from the barrel 10 of the compressed gas gun. Upon passing through high-pressure regulator 50 , compressed gas is fed both through gas transport tube 7 to the valve chamber 36 via manifold 8 , and through port 5 to the low pressure regulator 21 . Low-pressure regulator 21 is also generally known in the art. Compressed gas is regulated down to approximately between 50-125 p.s.i. by the low-pressure regulator, and is also adjusted by an externally accessible adjustment screw/cap 28 , which is preferably externally manually adjustable for easy and quick adjustment. Compressed gas then passes through port 25 into manifold 41 , where electro-pneumatic valve 30 directs it into cylinder housing 31 through low pressure passages 74 and low pressure gas pushes against first surface 72 on piston 32 , driving it rearwards and seating seal 70 against valve housing tip 35 . Note that piston's 32 movement in the rearward direction is limited by contact between the second surface 76 and a stop 34 a on the valve housing 34 .
This allows bolt tip 38 to clear the breech area of the body 3 , in which stage a projectile 100 moves from the feed tube 6 and rests directly in front of bolt tip 38 . The projectile is now chambered and prepared for firing from the breech. The high-pressure compressed gas, which has passed into the valve chamber 36 via high pressure passage 37 , is now pushing against valve pin 33 on the rear of piston 32 . The seal created by o-ring 70 on valve pin 33 is not broken because the force of the low-pressure gas on the first side of cylinder 31 is sufficient to hold the valve pin 33 rearward.
When trigger 24 is depressed, electro-pneumatic valve 30 is actuated (preferably using a solenoid housed within the manifold 41 , shutting off the flow of low-pressure gas to housing 31 and venting the housing 31 via manifold 41 . This allows the higher pressure gas, which is already pushing against valve tip 33 from the rear, to drive valve tip 33 forward to the firing position and break the seal 70 against the housing 35 . Bolt tip 38 , which is connected to piston 32 , pushes a projectile forward in the breech and seals the feed tube 6 from compressed gas during the first stage of launch because the valve pin 33 is still passing through valve housing tip 35 during this stage. This prevents gas leakage up the tube 6 and positions the projectile for accurate launch. Once the valve pin 33 clears the housing tip 35 , a flow passage D is opened, and the higher pressure gas flows through ports 32 a , 38 a drilled through the interior of piston 32 and bolt tip 38 and propels the paintball from barrel 10 . Note that the piston's 32 movement in the forward direction is limited by contact between the first surface 72 and a shoulder 73 within the cylinder 31 .
The signal sent to electro-pneumatic valve 30 is a momentary pulse, so when the pulse ceases, the valve 30 is de-actuated. This allows low-pressure gas to enter cylinder housing 31 and drive valve piston 32 rearwards against the force exerted by high-pressure gas to the seated position and allow loading of the next projectile.
Since piston 32 has a larger surface area on its outside diameter than the surface area on the valve pin 33 , low-pressure gas is able to hold high-pressure gas within the valve chamber 36 during the loading cycle of the gun. This is more advantageous than a design where a separate piston is used to actuate a separate valve, because the step of actuating and de-actuating the piston is removed from the launch cycle.
In addition, the pressures of the low pressure gas and high pressure gas may be varied according to user preference, thereby allowing for many variable pneumatic configurations of the gun and reducing problems with erratic cycling caused by using the same gas to control both the recock and launch functions of the gun. Because the mechanical sear is eliminated, the gun is also extremely lightweight and recoil is significantly reduced. The gun is also significantly faster than existing designs because the independent piston operation is eliminated.
In an alternate embodiment, the compressed gas gun can operate at one operating pressure instead of having a high-pressure velocity circuit and a low-pressure recock circuit. This is easily accomplished by adjusting the ratio of the surface sizes of the first surface 72 and the valve pin 33 . In this manner, the size of the gun is reduced even more because low-pressure regulator 21 is no longer needed.
FIGS. 6-11 show an alternate embodiment of the paintball marker that shares many elements in common with the marker in FIGS. 1-5 —the biggest difference between the embodiments being the inline cylinder 314 . Common elements between the inline cylinder 314 in FIGS. 6-11 and the cylinder 14 in FIGS. 1-5 have similar names and numbers between the embodiments and it should be appreciated that low pressure inlet passages 374 and high pressure inlet passages 341 correspond to the low and high pressure inlet passages 74 , 37 .
The marker of FIGS. 6-11 comprises a main body 3 , a grip portion 45 , a trigger 24 , a feed tube 6 , and a barrel 10 . The main body 3 comprises a bore 300 therethrough that slidably contains an inline cylinder 314 , which houses the paintball marker's firing mechanism.
When a user removes the mechanical linkage 400 from within the bores 302 , 402 as shown in FIGS. 10 and 11 , the user can slide the inline cylinder 314 from within the bore 300 . The mechanical linkage comprises two joined portions: the handle 404 and the locking pin 406 . The handle serves two purposes. First, pressing the handle 404 downwards in relation to the marker body, pulls the locking pin 406 from the bores 302 , 402 , which allows removal of the inline cylinder 314 . This removal can be done without the use of any specialty tools. Second, the convex area 408 serves as a “snatch grip,” which is well-known in the filed of paintball markers, and allows a marker to be safely carried during down times in a game—its specific purpose is that it allows transport of a marker without placing a user's hands and fingers near the trigger 24 where they might accidentally discharge the marker.
The locking pin 406 extends through the bores 302 , 402 to lock the inline cylinder 314 within the marker bore 300 , and prevent motion between the inline cylinder 314 and the marker. As best seen in FIGS. 8 and 9 , a spring 306 biases a button 304 rearwards into the groove 410 to hold the mechanical linkage 400 in place. Further, when high pressure compressed gas fills the firing chamber 308 , the compressed gas fills the chamber around the button 304 , which is sealed by seal 304 a , and drives the button 304 rearwards into the groove 410 with such force that a user cannot remove the mechanical linkage from the marker. This prevents the compressed gas from driving the inline cylinder 314 from the marker when it is pressurized.
It should be appreciated, from FIGS. 6, 6A, 7, and 7A particularly, that seals 350 , 352 , 354 , and 356 prevent leakage from the inline cylinder 314 through the bore 300 .
The operation of the inline cylinder 314 during the firing cycle will now be described. The control valve 30 directs low pressure compressed gas from low pressure regulator 21 through manifold 41 through the low pressure passages 374 to bolt chamber 331 allowing gas to contact first surface 332 a of piston 332 , driving the piston 332 rearward. Rearward movement of the piston 332 moves the valve pin 333 rearwards, which results in a seal between the seal 370 and the valve housing 360 . This is considered the loading position because the piston's tip 338 clears the breech 101 and allows a paintball 100 to drop into the breech 101 . (This loading position corresponds to the bolt position in FIG. 2 .)
Meanwhile, high pressure gas from the high pressure regulator flows through high pressure passage 341 , then through cylinder channels 339 , through governor channels 382 , into the governor chamber 380 , through firing chamber channels 384 , and into the firing chamber 308 . The low pressure compressed gas drives the piston 332 rearward, overcoming high-pressure gas pressure on valve pin 333 because the surface area of first surface 332 a of piston 332 is larger than that of the surface area 333 a of valve pin 333 . In this loading position shown in FIGS. 6, 8, 9, and 10 , the air flow into the firing chamber 308 is indicated by A.
As with the embodiment of FIGS. 1-5 , the control valve 330 preferably is a normally open three-way valve. When actuated in response to a trigger pull, the normally open valve will close its primary port and exhaust low pressure gas from the bolt chamber 331 through the low pressure passage 374 , releasing low pressure gas from the first surface 332 a of piston 332 . This allows high pressure compressed gas in the firing chamber 308 , pushing against the smaller surface area 333 a of valve pin 333 , to drive the pin 333 and bolt 332 forwards because of contact between the pin 333 and bolt 332 . This moves the o-ring 370 forwards of valve housing ports 335 , releasing the high pressure gas in the firing chamber 308 . The high pressure gas flows into the valve housing 360 around valve pin 333 , through ports 335 , into a piston passage 337 in piston 332 , and out through bolt tip channels 338 a in bolt tip 338 to launch a projectile 100 from the barrel 10 . In this firing position shown in FIGS. 7 and 7A , the air flow to fire the paintball is indicated by A.
The function of the inline cylinder 314 and gas governor 380 can best be appreciated in FIGS. 6, 6A, 7, and 7A . In FIGS. 6 and 6A , in the loading position, high pressure gas in the gas governor chamber 385 forces the gas governor pin 386 rearward, overcoming a forward bias of the gas governor pin from spring 306 . Upon firing, the forward movement of the valve pin 333 combined with the exhaust of the high pressure gas from the barrel 10 , allows the spring 306 to drive the gas governor pin 386 forwards to its maximum forward position shown in FIGS. 7 and 7A . In this forward position, the flow of high pressure gas into the firing chamber 308 is cut off because the gas governor pin 386 blocks gas governor ports 382 .
This high pressure cutoff results in a faster loading cycle, which begins when the normally open valve low pressure valve reopens and low pressure gas acts on the forward surface 332 a of bolt 332 . The cycle is faster because it does not have to overcome high pressure gas in the firing chamber 308 as the low pressure gas drives bolt 332 rearward, since there is no or little high pressure gas in the firing chamber 308 . As the low pressure gas drives the bolt 332 rearward, the valve 333 engages the gas governor pin 386 and drives it backwards to its position in FIGS. 6 and 6A .
The length of the governor pin 386 can also be manipulated to change the timing of the opening and closing of the governor without affecting the firing cycle.
While the present invention is described as a variable pneumatic sear for a paintball gun, it will be readily apparent that the teachings of the present invention can also be applied to other fields of invention, including pneumatically operated projectile launching devices of other types. In addition, the gun may be modified to incorporate a mechanical or pneumatic control circuit instead of an electronic control circuit, for instance a pulse valve or manually operated valve, or any other means of actuating the pneumatic sear.
It will be thus seen that the objects set forth above, and those made apparent from the preceding description, are attained. It will also be apparent to those skilled in the art that changes may be made to the construction of the invention without departing from the spirit of it. It is intended, therefore, that the description and drawings be interpreted as illustrative and that the following claims are to be interpreted in keeping with the spirit of the invention, rather than the specific details. set forth.
It is also to be understood that the following claims are intended to cover all the generic and specific features of the invention herein described and all statements of the scope of the invention that, as a matter of language, might be said to fall therebetween.
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A paintball marker has an inline cylinder that includes a gas governor that reduces gas flow from a compressed gas source to a valve area when the bolt is in a firing position; this increases efficiency in the marker because only the required air is used to fire the paintball. This bolt operates independent of the valve pin, which increases cycle speed and enables the governor to open and close at an optimum time in the firing cycle. Further, when the bolt/piston is recocking, the gap between the valve pin and governor valve pin enables low pressure gas driving the piston to start pressurizing the cylinder and driving the piston rearwards without resistance from the high pressure gas. The marker also allows a user to remove the inline cylinder without tools, and provides a convenient carrying handle for holding the paintball marker, which is commonly called a “snatch grip.”
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BACKGROUND
1. Field of Technology
Embodiments disclosed herein relate to audio systems, and more specifically to an audio system for reducing audio distortion of a loudspeaker.
2. Description of the Related Arts
A loudspeaker is a device that receives an electrical signal and converts the electrical signal to audible sound. Loudspeakers can include a voice coil that is inside of a magnet and is also attached to a diaphragm (e.g., a cone). When an electrical signal is applied to the voice coil, the coil generates a magnetic field that causes the voice coil and its attached diaphragm to move. The movement of the diaphragm pushes the surrounding air and generates sound waves.
For better sound fidelity, the sound waves produced by a loudspeaker should be proportional to the electrical signal applied to the loudspeaker. However, in a real loudspeaker, the movement of the diaphragm is not exactly proportional to the applied electrical signal, and this deviation leads to loss of acoustical fidelity. The loss of acoustical fidelity is especially pronounced with small loudspeakers, such as those found in mobile phones, tablet computers, laptops, and other portable devices.
There are several causes of the deviation between the electrical signal and the movement of the diaphragm. First, the coil and its associated parasitics are reactive and the magnetic field created by the coil varies depending on the frequency of the applied electrical signal. This results in a non-flat frequency response of the coil. Second, the effect of the magnetic field of the magnet on the coil is not constant as the position of the coil changes inside the magnet. As the coil moves backward and forward in response to the applied electrical signal, its position relative to the magnet changes. This changes the amount by which the magnetic field of the coil and the magnetic field of the magnet interact, resulting in movement of the diaphragm the extent of which is dependent upon the current position of the coil. Third, the springiness of the suspension supporting the diaphragm is not constant, and varies depending on how far it the diaphragm is displaced from its nominal position. All of these factors lead to increased distortion in the sound produced by a loudspeaker.
SUMMARY OF THE INVENTION
Embodiments disclosed herein describe an audio system that measures a test current through the loudspeaker as a way to measure the capacitance of the loudspeaker. The test current is used as feedback to generate a feedback signal that represents an actual displacement of the loudspeaker diaphragm. The feedback signal can then be used in a feedback loop to adjust a target audio signal, resulting in increased audio fidelity.
In one embodiment, the audio system comprises an audio driver configured to receive a target audio signal and a feedback signal and to generate an adjusted audio signal responsive to the target audio signal and the feedback signal. A loudspeaker is configured to convert the adjusted audio signal into acoustical sound. A test signal generator is configured to generate a test signal having a higher frequency than the target audio signal. The test signal also causes a test current to flow through the loudspeaker. A current sensing circuit is configured to measure the test current flowing through the loudspeaker and to generate a current sense signal indicative of the test current. A feedback circuit configured to generate the feedback signal responsive to the current sense signal. For example, the feedback circuit may be a look up table or a non-linear circuit that generates the feedback signal so that it represents an actual displacement of the loudspeaker.
In one embodiment, a method of operation in an audio system is disclosed. The method comprises generating an adjusted audio signal responsive to a target audio signal and a feedback signal; converting the adjusted audio signal into acoustical sound with a loudspeaker; generating a test signal having a higher frequency than the target audio signal, the test signal causing a test current to flow through the loudspeaker; measuring the test current flowing through the loudspeaker; generating a current sense signal indicative of the test current; and generating the feedback signal responsive to the current sense signal.
BRIEF DESCRIPTION OF THE DRAWINGS
The teachings of the embodiments disclosed herein can be readily understood by considering the following detailed description in conjunction with the accompanying drawings.
FIG. 1 is a physical diagram of a loudspeaker, according to one embodiment.
FIG. 2 is an electrical model of a loudspeaker 10 from FIG. 1 , according to one embodiment.
FIG. 3 is a simplified version of the electrical model from FIG. 2 at high frequencies, according to one embodiment
FIG. 4 is a block diagram of an audio system with reduced audio distortion, according to one embodiment.
FIG. 5 is a circuit diagram of an audio system with reduced audio distortion, according to one embodiment.
FIG. 6 illustrates signal waveforms of the audio system, according to one embodiment.
FIG. 7 is a circuit diagram of an audio system with reduced audio distortion, according to another embodiment.
FIG. 8 is a circuit diagram of an audio system with reduced audio distortion, according to yet another embodiment.
FIG. 9 is a physical diagram of a loudspeaker, according to another embodiment.
FIG. 10 is simplified electrical model of the loudspeaker from FIG. 9 at high frequencies, according to another embodiment.
FIG. 11 is a circuit diagram of an audio system with reduced audio distortion, according to a further embodiment.
DETAILED DESCRIPTION OF EMBODIMENTS
The Figures (FIG.) and the following description relate to various embodiments by way of illustration only. It should be noted that from the following discussion, alternative embodiments of the structures and methods disclosed herein will be readily recognized as viable alternatives that may be employed without departing from the principles discussed herein.
Reference will now be made in detail to several embodiments, examples of which are illustrated in the accompanying figures. It is noted that wherever practicable similar or like reference numbers may be used in the figures and may indicate similar or like functionality. The figures depict various embodiments for purposes of illustration only. One skilled in the art will readily recognize from the following description that alternative embodiments of the structures and methods illustrated herein may be employed without departing from the principles described herein.
Embodiments disclosed herein describe an audio system that measures a test current through the loudspeaker as a proxy for the capacitance of the loudspeaker. The test current is used as feedback to generate a feedback signal that represents an actual displacement of the loudspeaker diaphragm. The feedback signal can then be used in a feedback loop to adjust a target audio signal, resulting in a displacement of the speaker that more accurately matches the target audio signal, which increases audio fidelity.
FIG. 1 is a physical diagram of a loudspeaker 10 , according to one embodiment. Loudspeaker 10 includes a magnet 12 , a coil 14 , and a diaphragm 16 attached to the coil 14 . When an electrical signal is applied to the coil 14 , it causes the coil 14 to generate a magnetic field that interacts with the magnetic field of the magnet 12 . The coil 14 and the diaphragm 16 move back and forth to produce sound waves. If the coil 14 is closer to the center of the magnet 12 , the interaction between the magnetic fields is stronger. If the coil 14 is further from the center of the magnet 12 , the interaction is weaker. This changing magnetic field results in a non-constant force that creates acoustical distortion.
The coil 14 also generates an electric field 18 that interacts with the magnet 12 . The electric field 18 changes depending on the position of the coil 14 relative to the magnet 12 . Similar to the magnetic field, if the coil is in the center of the magnet 12 , the electrical field 18 interaction between the coil 14 and the magnet 12 is stronger. If the coil 14 moves away from the magnet 12 , the electric field 18 is reduced.
FIG. 2 is an electrical model of a loudspeaker 10 from FIG. 1 , according to one embodiment. Resistor R 1 and inductor L 1 model the moving coil 14 inside the loudspeaker 10 . Capacitor C 2 , inductor L 2 and resistor R 2 model the combined inertia of air, springiness of the diaphragm 16 , and induced electromotive force (EMF) caused by the movement of the coil 14 . The loudspeaker 10 also includes two speaker terminals through which electrical audio signals can be provided to the speaker.
Capacitor C 1 represents a self-capacitance of the loudspeaker 10 caused by the electric field 18 inside the loudspeaker 10 . C 1 varies with the movement of the coil 14 . When a positive voltage is applied to the coil 14 , it moves away from the magnet 12 , reducing the interaction of the electric field 18 with the magnet 12 and also reducing the capacitance of capacitor C 1 . When a negative voltage is applied to the coil 14 , it moves towards the magnet 12 , increasing the interaction of the electric field 18 with the magnet 12 and also increasing the capacitance of capacitor C 1 . Thus, the value of C 1 depends on the position of the coil 14 and diaphragm 16 and is directly linked to the acoustical sound generated by the loudspeaker 10 . In some embodiments, C 1 varies between 10 pF and 100 pF.
FIG. 3 is a simplified version of the electrical model from FIG. 2 at high frequencies, according to one embodiment. At high frequencies outside of the audio frequency range, such as 10 MHz, C 2 is assumed to be a short circuit and so C 2 , L 2 , and R 2 can all be removed from the circuit model. Resistor Rs represents the high frequency resistance of the loudspeaker 10 and corresponds to resistor R 1 from FIG. 2 . Inductor Ls represents the high frequency inductance of the loudspeaker 10 and corresponds to inductor L 1 from FIG. 2 . Capacitor Cs represents the self-capacitance of the loudspeaker 10 and corresponds to capacitor C 1 from FIG. 2 .
Embodiments of the present disclosure use the capacitance Cs of the coil 14 as a proxy for the displacement of the diaphragm 16 . The capacitance Cs can be measured and used as feedback to adjust the level of the electrical signal provided to the loudspeaker 10 , thereby compensating for deviations between the electrical signal and the displacement of the coil 14 and diaphragm 16 . As a result, the loudspeaker 10 has reduced distortion and better frequency response.
FIG. 4 is a block diagram of an audio system with reduced audio distortion, according to one embodiment. The audio system includes an audio driver 410 that receives a target audio signal 402 at its positive input and a feedback signal 408 at its negative input. In one embodiment, the target audio signal 402 is in an audible frequency range between 20 to 20,000 Hz and represents sound that is to be produced by the loudspeaker 10 . The audio driver compares the target audio signal 402 with the feedback signal 408 to generate an adjusted audio signal 404 . In one embodiment, the audio driver 410 may be an audio amplifier or include an amplification stage.
The compensation circuit 406 is coupled to an output of the audio driver 410 and a terminal 430 of the loudspeaker 10 . The compensation circuit 406 passes the adjusted audio signal 404 onto the loudspeaker 10 , which converts the adjusted audio signal 404 into acoustical sound. The capacitance of the capacitor Cs varies as the adjusted audio signal 404 is converted to acoustical sound by the loudspeaker 10 . The compensation circuit 406 also includes a test signal generator (not shown) that injects a high frequency test current into the capacitor Cs. A current level of the high frequency test current is measured and used as an indication of the instantaneous value of capacitor Cs. The measured current is converted to a voltage proportionate to the displacement of the diaphragm 16 , which is sent as the feedback signal 408 to the audio driver 410 . The loop gain of the audio driver 410 causes the target audio 402 and feedback signal 408 to eventually converge on one another. Since the feedback signal 408 can be an accurate representation of the actual acoustical sound produced by the loudspeaker 10 , this ensures that the generated acoustical sound is similar to the target audio signal 402 , thereby increasing the fidelity of sound produced by the loudspeaker 10 .
The bottom terminal 432 of the loudspeaker 432 is coupled to ground to provide a discharge path for signals input to the loudspeaker via the top terminal 430 . In other embodiments, the compensation circuit 406 can also be coupled to the bottom terminal 432 of the loudspeaker 12 or a power supply input of the audio driver 410 , as will be explained herein. In other embodiments, the audio driver 410 can be a differential driver instead of a single ended driver.
FIG. 5 is a circuit diagram of an audio system with reduced audio distortion, according to one embodiment. The compensation circuit 406 includes a test signal generator 506 that generates an alternating current (AC) test signal 508 . The test signal 508 oscillates at a higher frequency than the audio frequency range of the target audio signal 402 . For example, the test signal 508 can have a frequency of 10 MHz, which is well above the 20 hz-20 khz range of the target audio signal 402 . In one embodiment, the test signal 508 can have a substantially fixed voltage amplitude and a substantially fixed frequency. However, the current of the test signal 508 may vary as the loudspeaker 10 produces acoustical sound.
A combiner circuit 510 is coupled to the output of the audio driver 410 and a terminal 430 of the loudspeaker 10 . The combiner circuit 510 combines the test signal 508 with the adjusted audio signal 404 to generate a combined signal 502 that is provided to the loudspeaker 10 . Combiner circuit 510 may include an inductor L 3 and a capacitor C 3 . Inductor L 3 is selected to pass audio frequencies but to block the frequency of the test signal 508 . L 3 prevents the current of the test signal 508 from flowing through output of the audio driver 410 . Capacitor C 3 is selected to block audio frequencies but to pass the frequency of the test signal 508 . Capacitor C 3 prevents the adjusted audio signal 404 from affecting current measurement of the test signal 508 .
The combined signal 502 , which includes both an adjusted audio signal portion and a test signal portion, is provided to the top terminal 430 of the loudspeaker 10 . The adjusted audio signal portion causes the coil 14 of the loudspeaker 10 to move back and forth, thereby producing acoustical sound that is audible to a listener. The test signal portion of the combined signal 502 generates a test current through the capacitance Cs but does not cause the loudspeaker to produce acoustical sound. Substantially all of the test current for the test signal portion flows through the capacitor Cs and not inductor Ls. This is because the test signal portion operates at a high frequency, and inductor Ls is an open circuit at high frequencies.
The capacitance Cs changes over time as the coil 14 moves back and forth to produce acoustical sound. Because Cs changes and the test current of test signal 508 flows through Cs, the current level of the test signal 508 is dependent on Cs and changes as the value of Cs changes. Thus, when the coil 14 moves further from the magnet, the capacitance Cs decreases and so does the current level of the test signal 508 . As the coil 14 moves towards the magnet, the capacitance Cs increases and so does the current level of the test signal 508 .
Current measuring circuit 520 is coupled between the test signal generator 506 and the signal combiner 510 . Current measuring circuit 520 measures the current level of the test signal 508 (which can have a fixed voltage amplitude and varying current) and generates a current sense signal 512 indicating the measured current level of the test signal 508 . The current measuring circuit 520 may include, for example, a series resistor that is coupled between the test voltage generator 506 and the signal combiner 510 , as well as a differential amplifier to amplify a voltage difference across the resistor.
Amplitude detector 514 receives the current sense signal 512 and detects the amplitude of the current sense signal 512 . The amplitude detector 514 then generates a current amplitude signal 516 that represents the time varying amplitude of the current sense signal 512 . As the current level of the test signal 508 is tied to the capacitance Cs of the loudspeaker 10 , the instantaneous level of the current amplitude signal 516 also represents the instantaneous capacitance Cs of the loudspeaker 10 . In one embodiment, the amplitude detector 514 includes a diode D 1 and a capacitor C 4 coupled to the output of the diode D 1 . Diode D 1 acts as a half-wave rectifier and capacitor C 4 smoothes the half-wave rectified signal to generate the current amplitude signal 516 .
The feedback circuit 518 is coupled to the output of the amplitude detector 514 and receives the current amplitude signal 516 . The feedback circuit 518 converts the current amplitude signal 516 into a feedback signal 408 that represents the extent of displacement of the diaphragm 16 . In one embodiment, the feedback circuit 518 includes a look up table that maps values for the current amplitude signal 516 to displacement values representing the extent of displacement of the diaphragm 16 . The displacement values are then converted into voltages that are output as the feedback signal 408 . In one embodiment, the mapping between the current amplitude signal 516 and the diaphragm 16 displacement may be determined in advance through actual measurements of the diaphragm 16 displacement and current amplitude signal 516 , which are then stored into the look up table.
In other embodiments, the feedback circuit 518 can be a non-linear circuit that converts the current amplitude signal 516 into a feedback signal 408 that represents an approximate extent of the diaphragm 16 displacement.
The audio driver 410 receives the feedback signal 408 and compares the feedback signal 408 to the target audio signal 402 to adjust a level of the adjusted audio signal 404 . The loop gain of the audio driver 410 causes the target audio signal 402 and feedback signal 408 to eventually converge onto one another, thereby ensuring that the acoustical output of the loudspeaker 10 matches that of the target audio signal 402 .
FIG. 6 illustrates signal waveforms of the audio system from FIG. 5 , according to one embodiment. Signal waveforms are shown for the adjusted audio signal 404 , the test signal 508 , the current sense signal 512 , and the current amplitude signal 516 . The adjusted audio signal 404 is a time-varying voltage signal that causes the voice coil 14 to move back and forth to produce acoustical sound. The movement of the coil 14 creates variations in the capacitance Cs of the loudspeaker 10 . The test signal 508 has a substantially constant frequency and voltage amplitude. However, the current level of the test signal 508 , represented by the current sense signal 512 , changes as the capacitance Cs changes. The changing current of the test signal 508 is captured in the voltage level of the current sense signal 512 . Finally, the current amplitude signal 516 is the time varying amplitude of the current sense signal 512 and is indicative of the changing current amplitude of the test signal 508 and tracks the changing capacitance Cs of the loudspeaker 10 .
FIG. 7 is a circuit diagram of an audio system with reduced audio distortion, according to another embodiment. The audio system of FIG. 7 is similar to the audio system of FIG. 6 , except that the current detector circuit 520 is now coupled to the other terminal 432 of the loudspeaker 10 . Current detector circuit 520 still detects a level of a test current flowing through the capacitor Cs but performs the measurement in a slightly different manner.
Specifically, current detector circuit 520 detects a current of the combined signal 502 . The current of the combined signal 502 includes both audio frequency components of the adjusted audio signal 404 , as well a high frequency component of the test signal 508 . To separate the audio frequency components from the high frequency component of the test signal 508 , current detector circuit 520 includes a series capacitor C 5 . Capacitor C 5 acts as a high pass filter that filters out the audio frequency components of the detected current but passes the frequency components of the test signal 506 . As a result, current sense signal 512 indicates a current level of the test signal 508 but not the adjusted audio signal 404 . In other embodiments, capacitor C 5 may be placed between the current detector circuit 520 and the loudspeaker 10 to filter out the audio frequency components before detecting the current level of the test signal 508 .
FIG. 8 is a circuit diagram of an audio system with reduced audio distortion, according to yet another embodiment. The audio system of FIG. 8 is similar to the audio system of FIG. 7 , except that test signal generator 506 is now coupled to a power supply input of the audio driver 410 and indirectly causes a high frequency test current to flow through the speaker 10 by varying the power supply input to the audio driver 410 .
As shown, the audio driver 410 is powered by a DC supply 802 , such as a battery or other power source. The test signal generator 506 generates a test signal 508 which is combined with the DC supply 802 via capacitor C 6 to generate an adjusted power supply voltage 804 . The adjusted power supply voltage 804 has both a DC component from the DC supply voltage 802 and an AC component from the test signal generator 506 . The AC component of the power supply signal 804 varies the output of the audio driver 410 and causes the adjusted audio signal 404 to have a high frequency AC component that matches the frequency of the test signal 508 .
The high frequency AC component of the adjusted audio signal 404 causes a high frequency test current to flow through capacitor Cs of the loudspeaker 10 . The current detection circuit 520 measures a current level of the test current. The level of this test current is reflected in the current sense signal 512 , amplitude detected by the amplitude detector circuit 514 to generate a current amplitude signal 516 , and then used by the feedback circuit 518 to generate the feedback signal 408 . The embodiment of FIG. 8 may be simpler to implement than the previous embodiments of FIG. 5 and FIG. 7 due to the lack of a combiner circuit 510 and its associated discrete components.
FIG. 9 is a physical diagram of a loudspeaker 10 , according to another embodiment. The physical diagram of FIG. 9 is similar to that of FIG. 1 , but now includes a printed circuit board (PCB) ground plane 902 . The PCB ground plane 902 may be, for example, for a PCB that the loudspeaker 10 is mounted to. In other embodiments, the PCB ground plane 902 may be replaced with another grounded object that is adjacent to the loudspeaker 10 . The coil 14 also has an electric field 904 that interacts with the ground plane 902 of the PCB. The strength of the electric field 904 changes as the coil 14 and diaphragm 16 move back and forth to produce acoustical sound.
FIG. 10 is simplified electrical model of the loudspeaker 10 from FIG. 9 at high frequencies, according to one embodiment. The loudspeaker model from FIG. 10 is similar to the loudspeaker model from FIG. 3 , but now the model includes a capacitor Cg in place of capacitor Cs. Capacitor Cg is connected to ground and represents the electric field 904 between the coil 14 and the PCB ground plane 902 . The capacitance of capacitor Cg also changes as the coil 14 and diaphragm 16 move back and forth to produce acoustical sound.
FIG. 11 is a circuit diagram of an audio system with reduced audio distortion, according to a further embodiment. At a functional level, the audio system of FIG. 11 uses capacitance Cg as a proxy for the displacement of the diaphragm 16 . The audio system measures a current through the capacitance Cg and uses the current to generate feedback signal 408 for adjusting the level of the adjusted audio signal 404 , thereby compensating for deviations between the target audio signal 402 and the actual displacement of the diaphragm 16 .
At a circuit level, the audio system of FIG. 11 is similar to the audio system of the FIG. 5 but now includes a differential audio driver 1110 that outputs a differential adjusted audio signal 1104 . Signal combiner 1112 is also different and now includes two inductors L 3 and L 4 coupled between the outputs of the audio driver 1110 and the loudspeaker 10 . Inductors L 3 and L 4 are chokes that block the test signal 506 from flowing back through the outputs of the audio driver 1110 .
Signal combiner 510 combines test signal 508 with the differential adjusted audio signal 1104 to generate a differential combined signal 1102 . The adjusted audio signal portion of the combined signal 1102 is converted to acoustical sound by the loudspeaker 10 . Capacitor Cg changes as the loudspeaker 10 produces acoustical sound. The test signal 506 is blocked by inductor L 4 and L 3 , and so the only discharge path available to the test signal 506 is through capacitor Cg. The current sensing circuit 520 measures the current level of the test signal 506 , which represents the amount of test current flowing through capacitor Cg. Current sensing circuit 520 then generates current sensing signal 512 to indicate a current level of the test signal 506 .
Amplitude detector 514 detects an amplitude of the current sense signal 512 and generates a current amplitude signal 516 . Feedback circuit 518 receives the current amplitude signal 516 and uses the current amplitude signal 516 to generate a feedback signal 408 . In one embodiment, feedback circuit 518 uses a look up table that maps levels of the current amplitude signal 516 to displacement values that are used to generate the feedback signal 408 . The look up table for the feedback circuit 518 in FIG. 11 may have different values than the look up table for the feedback circuit 518 in FIG. 5 .
Audio driver 1110 receives the target audio signal 402 and the feedback signal 408 and generates the differential adjusted audio signal 1104 by comparing its two input signals. The resulting adjusted audio signal 1104 compensates for deviations between the target audio signal 402 and the actual movement of the loudspeaker diaphragm 16 . As a result, the displacement of the speaker diaphragm 16 matches that of the target audio signal 402 to increase the audio fidelity of the audio system.
Upon reading this disclosure, those of skill in the art will appreciate still additional alternative designs for reducing audio distortion in an audio system. Thus, while particular embodiments and applications have been illustrated and described, it is to be understood that the embodiments discussed herein are not limited to the precise construction and components disclosed herein and that various modifications, changes and variations which will be apparent to those skilled in the art may be made in the arrangement, operation and details of the method and apparatus disclosed herein without departing from the spirit and scope of the disclosure.
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An audio system comprises an audio driver configured to receive a target audio signal and a feedback signal and to generate an adjusted audio signal responsive to the target audio signal and the feedback signal. A loudspeaker is configured to convert the adjusted audio signal into acoustical sound. A test signal generator is configured to generate a test signal having a higher frequency than the target audio signal. The test signal causes a test current to flow through the loudspeaker. A current sensing circuit is configured to measure the test current flowing through the loudspeaker and to generate a current sense signal indicative of the test current. A feedback circuit is configured generates the feedback signal responsive to the current sense signal.
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TECHNICAL FIELD
This invention relates to infant carrier and receiving base in combinations as well as individually. The receiving bases employ common latching aspects utilizing releasable securing positioning of the carrier in any number of bases. One specific embodiment is for use as an infant car seat or more precisely, an infant carrier that when combined with a base becomes an infant car seat. Another embodiment is for use as an infant carrier in combination with a carriage stroller.
BACKGROUND OF THE INVENTION
Infant carriers are well-known and used to easily carry an infant from place-to-place as well as seating for an infant for feeding or playing. These carriers are generally a plastic shell with a seating surface, sides, an adjustable carry handle, rocker-shaped bottom runners, a restraint harness, a carry handle and a pad.
Infant carriers are often used as infant car seats either by themselves, or with the addition of a base. If the carriers are used as a car seat by themselves, they have hooks of some kind which can be used to secure them to an automobile seatbelt. If they are used with a base, the base has a somewhat torso-shaped contour over which an automobile seatbelt is passed to secure the base in the automobile. The carrier is then attached to the base in some way.
Infant car seats have progressed over the years. The first infant car seat was little more than a double-walled plastic dish pan (the GM® Loveseat). Evenflo advanced the state-of-the-art with a lightweight infant car seat with an adjustable angle (the Dyn-o-mite™). Century followed with an infant car seat with a carry handle and a stay-in-the-car base (the Century® 580). Other manufacturers have also added improvements as they introduced new models. The various seats have provided good protection in transporting children in automobiles.
Despite the advances, however, infant car seats are not as safe or easy to use as they might be. For example, changing the shoulder belt height on most seats means unthreading a complex belt system and rethreading through a different set of slots, which is a difficult task for people who are not mechanically inclined. Additionally, nearly every infant car seat has been recalled because their handle lock mechanisms were not strong enough and jumped position. It has been reported that misuse of infant car seats continues to be a major problem and current seats are too complex. Finally, most infant car seats require removal of the infant carrier from the base to adjust the infant carrier back angle, which means the user is trying to adjust a back angle that is not currently visible.
This invention was developed to continue to advance the state-of-the-art for infant car seats. It attempts to make an infant car seat that is easier to understand, easier to use, and safer.
SUMMARY OF THE INVENTION
The invention comprises an infant carrier and a mating base which combine to form an infant carrier/car seat combination. The infant carrier can be used by itself as an infant carrier, but it is made to be very lightweight and must be used with its companion base, which is heavier and more structural, to become an infant car seat. This combination infant carrier/car seat combination, like other infant carriers, has a seat, a back and side walls. It also has belt slots which will accommodate a 3-point or a 5-point harness system. It has a carry handle attached to the central upper side walls and a means to adjust the position of the carry handle. It also has either a 3-point harness system which comprises a crotch belt with a buckle and two shoulder belts, or a 5-point harness system which comprises a crotch belt with a buckle and left and right lap/shoulder belts which attach to the crotch belt buckle. It also has a means to adjust the location of the slots in the seatback where the shoulder belts pass through as well as a means to adjust the belt length of the lap/shoulder belts. Further, it has runners on its bottom to allow a rocking motion when the carrier is placed on a flat surface and to mate with a contour in a matching base when the carrier is used with the base. In addition, it has a mechanism to cooperate with the base to removably secure the carrier and the base together.
The base of this invention has an upper contour which matches and receives a portion of the runners on the carrier so as to locate the carrier relative to the base and to help secure it to the base by preventing side-to-side movement and front-to-back movement. The base also has components which cooperate with a mechanism in the carrier to complete removable attachment of the two by preventing vertical movement of the carrier relative to the base. The base also has a bottom contour which rests on an automobile seat and which is adjustable to elevate or lower one end of the base, and thus to control the angle of the base relative to horizontal in a front-to-back direction. The adjustment is achieved by turning a knob on the back of the base, which through a mechanism, adjusts the base bottom contour. The base also has a somewhat torso-like contour near its front to accept at least the lap portion of an automobile seatbelt and which can also accommodate a standard LATCH (Lower Anchors and Tethers for CHildren) belt system, a specialized belt mandated by FMVSS (Federal Motor Vehicle Safety Standard) 225 to attach children's car seats to automobile seats and the corresponding top tethers and lower attachments identified in FMVSS 213. Finally, the base optionally has a lock-off which can squeeze and deform the automobile lap seatbelt and/or lap/shoulder seatbelts thus securing them to the base.
The belt slots in the back of the carrier, through which the shoulder belt portions of the 3-point or 5-point harness pass are moveable up or down on the back of the infant carrier. This movement is achieved by penetrating or cutting away the back of the carrier in any area it would be desirable to have the belts pass through the back of the carrier. The result of this cutting away is two elongated slots, somewhat wider than the shoulder belts and running from the lowest desired position (plus any clearances required) to the highest desired position. A movable panel with left and right belt slots is located behind the carrier seat back and is slidably retained on the carrier back. Left and right belt slots on the panel correspond to the elongated slots in the carrier seatback.
The movable panel is sized so that there is enough extra material above its belt slots and enough extra material below the belt slots so that whatever position the movable panel is in, the elongated slots in the carrier seatback are always covered. The height of the movable panel, and thus of the shoulder belt slots, is controlled by locating the movable panel relative to the elongated slots in the carrier seatback. This is achieved by mounting a spring-biased plunger onto the rear movable panel and letting it penetrate at least one of several locating openings in the carrier seatback. In one specific embodiment of the invention, multiple plungers engage multiple openings. To move the belt slots from one position to another, one must simply pull the plunger to disengage it with the opening in the carrier seatback, move the movable panel to the desired position and release the plunger to allow it to re-engage with a different opening in the carrier seatback.
The carry handle pivots on an axis running across the carrier from side-to-side and is located by a hub projection on each side of the carrier which rotationally engages a mating hub on each corresponding end of the carry handle. Each carry handle hub is equipped with an outwardly spring-biased plunger which is rotationally constrained but which is allowed to slide normal to the plane of the carry handle, and each plunger is equipped with a projecting pin which extends into its corresponding carrier hub. Each carrier hub has a segment of a gear with inwardly-facing teeth such that the pins on the carry handle plungers can engage with a space between two teeth on corresponding gear segments. When the pins on the spring-biased plungers are in their normal position, carry handle rotation is prevented. When the spring-biased plungers are pushed in, the projecting pins clear their neighboring gear teeth in the carrier hubs and the handle is free to rotate. When the spring-biased plungers are released, the projecting pins again, engage the gear teeth.
A problem with many handle positioning mechanisms as currently manufactured is that they are usually made of plastic which can deform and allow the pin and gear teeth to jump position. A further disadvantage of plastic in current construction is that to achieve strength, the plastic gear segment and the plunger must be thick. Since they are thick, they do not lie coplanar or even nearly coplanar and thus must resist twisting forces on themselves as well as rotational forces on the handle. This invention substitutes a more rigid material such as steel or aluminum for the gear teeth in the carrier hubs. While it is not absolutely essential that steel or aluminum be substituted for plastic, it is important that the gear teeth and mating control mechanisms are made thin and nearly planar.
A second problem of current designs is, as noted above, that the plunger and its pin which engages the gear teeth tends to twist sideways when a rotational force is applied to the carrier handle, because the plunger with its pin and the gear segment on the carrier hub cannot lie in the same plane. In this invention, an additional steel or aluminum guiding plate is fixed to the inside of each carry handle hub between the corresponding plunger in the carry handle hub and the gear teeth in the corresponding carrier hub. The guiding plate has an elongated opening through which the pin of the plunger projects. The elongated opening is sized to allow movement of the plunger and its projecting pin from their maximum outward position where the pin engages its corresponding gear segment to its maximum inward position where the pin is clear of its corresponding gear segment and the handle may rotate. Since the guiding plate is very close to its corresponding gear segment, most twisting of the plungers is eliminated and a more robust and reliable mechanism is achieved.
The base of the infant carrier/car seat has an upper contour to match and receive a portion of the runners on the carrier. The contour locates the carrier shell front-to-back and side-to-side. The base also has at least two steel blades projecting from its surface in a relatively central front-to-back location and located side-to-side to penetrate openings in the runners of the carrier. Each of these blades has a slanted top edge and a recess or hook on its trailing edge. The runners on the carrier each have an opening to receive a corresponding blade. When the carrier is located on the base, the blades project into the carrier. A steel bar located in the carrier in the area of the hooks and extending from one side of the carrier to the other and well past the sides of the blades is spring-biased into the hooks on each respective blade. It can be seen that when the steel bar inside the carrier is engaged in the hooks penetrating the carrier, the two are fastened securely together. The steel bar is loosely connected to a puller near each of its ends and that puller is connected to a common sliding handle on the outside of the carrier. Pulling the sliding handle on the outside of the carrier pulls the pullers which, in turn, pull the steel bar, overcome the spring bias, and move the steel bar free of the hooks in the blades extending from the base. The carrier can then be removed from the base.
If the carrier is set into the base, it is guided into position by the mating contours of the runners and the upper base surface. As the carrier moves downward, the steel blades penetrate the carrier runners, and the slanted upper surface of the steel blades move the steel bar rearward overcoming the spring bias until the carrier is fully seated in the base. When the carrier is fully seated, the hooks in the steel blade align with the steel bar and the spring bias moves the steel bar into a latched position, again locking the carrier and the base together.
The bottom contour of the base is divided into two portions, a fixed portion in the rear and a movable portion in the front. The movable portion is telescopically mounted near the front of the base and can move into or out of the base thus changing the base angle relative to the seating angle. The moving portion of the base telescopes into the base at its front from an extended position to a position nearly flat to the fixed portion of the base.
When the base is on an automobile seat, the base recline angle can be controlled by controlling the position of the telescoping moving base. The first element of the position controlling mechanism is an axle extending from near the front of the base to beyond the rear of the base. A knob is fixed to the rear of the axle to allow turning of the axle, and a screw thread is fixed to the opposite end. A moving nut or follower is engaged on the screw thread such that it cannot rotate but must move forward or backward as the axle is turned with the knob. The follower has two lateral cylindrical projections extending from each side, each projection in contact with an inclined plane attached to the telescoping moving base. Therefore, longitudinal front-to-back axial movement is translated into vertical movement by impingement of the cylindrical projections of the cam follower on the inclined plane of the moving base which drives the moving base into or out of the base. The advantages of this system are its infinite adjustment and its accessibility even when the carrier is on the base.
The base of the infant carrier/car seat combination has a torso-like path for the automobile seat belt or LATCH belt. On most carrier bases, there is no further connection between the base and the automobile or LATCH belt. This base is provided with a lock-off located in the belt path to more firmly secure the automobile seat belt to the base and help prevent any sideward relative sliding between the base and the automobile seat belt. The lock-off further aids in securing the base when the automobile lap/shoulder belt has a free-sliding latch plate and an emergency locking shoulder belt by clamping the lap and shoulder belts together and minimizing potential movement between them. The lock-off includes a transverse groove in the base in the central part of the belt path. A raised rib with a knurl is positioned in the center of the transverse groove. A hollow channel lock-off beam is pivotally attached to base at one end of the transverse groove through apertured openings in the beam channel through which is inserted a pivot pin captured within a pivot housing. Movement of the beam is pivotal from an open position to a closed position where it is essentially parallel to the transverse groove.
The lock-off beam can be secured in the second, essentially parallel position by any of several means, the preferable being a spring-loaded plunger on its free end whereby the spring-loaded plunger has a protruding lip which can engage a similar reversed lip in the base. The lock-off beam is provided with left and right extending walls which fall in the transverse groove in the base on either side of the knurled rib in the transverse groove. When the automobile seat belt (or seat belt and combined shoulder belt) are captured between the transverse groove and the extending walls of the lock-off beam, they are forced into a “W” form and pushed into the knurled rib thus greatly diminishing the ability of the seat belt(s) to move relative to the base.
A mounting and storage component is provided for the LATCH belts when required to be supplied with infant car seats. This solves the LATCH belt storage problem by making pockets on either side of the base adjacent to the belt path. The pockets have securing sockets and the LATCH belt ends are secured into these sockets. When the LATCH belt ends are stored, the belt path is entirely free to use a standard automobile seatbelt.
It is an object of this invention wherein the mechanism controlling the handle angle uses an intermediate plate with an elongated slot to greatly increase handle strength and reliability.
It is another object of this invention wherein the method of adjusting the shoulder belt height uses an external moving panel which is intuitive, simple and requires no rethreading of belts and no hard components in the infant seating area.
It is still another object of this invention wherein the infant seat to base attachment uses a simple, reliable and strong two or more point attachment combined with a locating “bucket.”
It is still yet another object of this invention to provide a means of achieving angular adjustments of the base wherein the adjustment means is accessible when the infant car seat is installed in an automobile with the infant seat installed on the base.
It is a further object of this invention to provide child harness belts which are easily removable.
In comparison to Prior Art devices which use a plunger and teeth arrangement to control the handle angle, most of which have not been strong enough and have been recalled, none uses metal-to-metal engagement, and none use an intermediate plate to reduce twisting of the locking plunger.
Wherein most infant carriers use simple slots which require belt rethreading to change the belt position, and others use elongated slots with sliding plates, none uses an external sliding panel secured to the exterior of the infant carrier which is easy to use and has no component on or near the seating surface.
Wherein many infant carriers use a rear release handle on the carrier or base in which to attach infant seats to bases, and while most have mating hooks and latches of some sort, none have at least a pair of notched metal plates protruding from a recessed locating bucket which are engaged by a metal axle and whereby the axle is released from the notched metal plates by a release handle mounted to the exterior of the infant carrier such that the natural motion of picking up the infant carrier is compatible with and encourages the movement required to release the infant carrier from the base.
Wherein other manufacturers use multiple methods to achieve angular adjustment, and wherein for example, Graco uses a pivoting front base with an inconvenient latching means which is not accessible when the base is installed and is limited to three positions, and whereas Evenflo uses a screw adjustment which is flimsy and not accessible with the seat installed, and further wherein others use flipper panels which are limited to two positions and require removal of the base to adjust, none of these methods offers the convenience afforded by an externally driven adjustable front foot of the present invention.
And wherein others have harnesses that are removable for washing for example, none is removable by simply folding out two belt retainers as shown and illustrated on the present invention.
The invention as described below is different from the above devices in at least the following aspects: (a) the metal-to-metal mechanism with an intermediate plate is stronger and very reliable; (b) the rear-mounted belt height adjuster panel is very easy to understand and use, others are not; (c) the rear, centrally mounted belt height adjuster is operated entirely from the rear of the seat and the means of operation is compatible with and encourages the intended result; (d) the base angle adjustment is infinite and accessible when both the base and the infant seat are installed in an automobile and does not require removal of the auto seat belt or LATCH belt to allow adjustment; and (d) the harness retention system is simple and easy-to-understand and thus is less likely to be used incorrectly.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may take physical form in certain parts and arrangements of parts, a preferred embodiment of which will be described in detail in the specification and illustrated in the accompanying drawings which form a part hereof, and wherein:
FIG. 1 is a front perspective view of the infant carrier positioned in its base for use as an infant car seat;
FIG. 2 is a top perspective view of the infant carrier of FIG. 1 removed from its base for use as an infant carrier;
FIG. 3 is a bottom rear perspective of the infant carrier of FIG. 2 ,
FIG. 3 a is an exploded view of the belt height adjustment panel in its upper position illustrated in FIG. 3 ;
FIG. 3 b is a bottom rear perspective view of an alternative embodiment of the infant carrier of FIG. 2 illustrating rear belt length adjustment and also showing the belt height adjustment panel in its lower position;
FIG. 4 is a top perspective view of the interior of the plastic shell of the infant carrier of FIG. 2 with its foam liner and adjuster bezel removed;
FIG. 5 is a partial bottom view of the belt retention means;
FIG. 6 is an assembly view of the infant carrier release mechanism and the infant shoulder belt adjustment mechanism;
FIG. 7 is an enlarged cross-sectional view of a portion of the shoulder belt adjustment mechanism taken along line 7 - 7 of FIG. 6 ;
FIG. 8 is an enlarged view of the handle hubs of the infant carrier with hub covers removed on each hub;
FIG. 8 a is an enlarged partial fragmentary assembly view of the handle hubs with outer handle hub housing removed;
FIG. 9 is an assembly view of the gear segment mechanism of the hubs of FIG. 8 ,
FIG. 10 is a top perspective view of the infant base;
FIG. 11 is an enlarged cross-sectional view of the belt lock-off taken along line 11 - 11 of FIG. 10 ;
FIG. 12 is a fragmentary top perspective view of the belt lock-off in its open position;
FIG. 13 is a front perspective view of the infant base illustrating LATCH belts;
FIG. 14 is an assembly view of the base with the top of the base removed to illustrate the height adjustment mechanism
FIG. 14 a is an exploded fragmentary assembly view of the base with its top removed and one inclined plane removed illustrating one cylindrical projection of the cam follower used to effect vertical movement of the movable portion of the base which is visible;
FIG. 14 b is a side view of the infant carrier and base with the movable portion in its retracted position positioned on a rear automobile car seat showing a more upright infant seating position;
FIG. 14 c is a side view of FIG. 14 b with the movable portion in its extended position on a rear automobile car seat showing a more reclined infant seating position;
FIG. 15 is a bottom partial fragmentary view of one of the base LATCH belt storage and securing compartments; and
FIG. 16 is a front perspective view of an infant carrier positioned above a carriage stroller prior to fastening engagement with a pair of forwardly-facing upwardly-extending J-shaped hooks, the carrier illustrated with belt restraining web removed.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings wherein the drawings are for purposes of illustrating the preferred embodiment of the invention only and not for purposes of limiting the same, the figures show a separable infant carrier/car seat combination. The infant carrier may be used alone to carry or seat an infant, or in combination with a base to transport an infant in an automobile. The infant car seat has two main components; an infant carrier and a base into which the infant carrier fits and is removably secured. The base consists of a platform with a seat receiving contour which at least partially mates with the bottom of the infant seat, a set of automobile seatbelt receiving openings on its left and right sides, and a bottom panel, part of which is fixed, and part of which is movable by an angle adjusting means to adjust the angle of the base when it is positioned on an automobile seat. Further, the base cooperates with the removable securement means of the infant carrier to allow the infant carrier to be either attached or released from the base.
The infant carrier/car seat combination 10 has a removable infant carrier component 20 with adjustable carrying means 70 and child restraining means 50 in combination with a releasably mating receiving base 40 for securing the carrier component therein. FIG. 1 illustrates infant carrier/car seat 10 in combination with child restraining means 50 (interchangeably referred to as a restraint harness) positioned in its upper position through its threading engagement with belt height positioning means 80 while FIG. 2 illustrates the infant carrier removed from receiving base 40 and the child restraint harness illustrated in its lowered position. As shown in those figures, removable infant carrier 20 has an outer plastic shell 88 with an upper plastic seat back region 22 and lower plastic seat region 24 . This outer plastic shell is optionally at least partially lined with a foam inner liner 92 having a bottom seating surface 14 with left 16 a and right 16 b curvilinear foam carrier seat raised sides, and a back surface 12 with left 18 a and right 18 b curvilinear foam carrier back side panels, the designation left and right being determined from the perspective of a viewer looking toward the infant carrier/car seat base with its seating surface in closest proximity to the viewer. The infant seat is formed of a molded plastic shell lined with an expanded polystyrene foam liner, much like a helmet. The plastic shell and expanded foam are secured to each other by mechanical means or an adhesive or combinations thereof, so that they act cooperatively to produce a more rigid structure.
The outer contour of molded foam inner liner 92 at least partially approximates the inner contour of outer plastic shell 88 and has a thickness so that its inner contour becomes the inner seating surface, back surface, and sides of the infant carrier. The foam liner serves to attenuate impact forces, reduce the likelihood of penetration of the shell, and provide a more contiguous seating surface than the molded seat shell. Foam densities and energy absorbing properties can be varied by the particular foam material and formulation selected.
Infant carrier 20 also has an adjustable carrying means 70 which includes carry handle 74 pivotable about right 78 b and left 78 a hubs with optional foam covering 76 affixed about at least a portion of the handle. Child restraining means 50 includes a harness system including buckle 60 , seatbelt webbing (variously 54 , 56 a , 56 b , 58 a , 58 b ), means to adjust the shoulder belt height 100 for various sized infants through hour-glass slots 64 in the foam inner liner 92 as well as corresponding hour-glass slots 34 in outer plastic shell 88 , and means to adjust the harness length 82 for various sized infants. Securing engagement of one end of the child seatbelt webbing includes means to fasten buckle 60 in the infant carrier through slotted buckle web opening 86 using crotch strap 54 as well as child lap belt webbing retaining means through side seat slotted openings 72 for the left 56 a and right 56 b child lap belts. FIG. 1 and FIG. 2 illustrate a five-point harness system consisting of crotch strap 54 in conjunction with child shoulder belts 58 a , 58 b which are contiguous with child lap belts 56 a , 56 b by threading through apertured buckle inserts 62 a , 62 b respectively. In a three-point harness system, the child lap belts are not present. Slotted child shoulder belt positioning means 66 is optionally threadably engaged with left 58 a and right 58 b child shoulder belts. Belt length adjustment means 84 is positioned toward a front center of the carrier with trim bezel 82 and slotted opening 90 for length adjustment web 52 which through its interconnectivity with the other child restraint belts in the rear of the carrier will simultaneously adjust the fit of these belts as well.
As better illustrated in FIG. 2 and FIG. 3 , illustrating infant carrier 20 removed from its receiving base 40 , the infant carrier has generally curved arcuate runners 96 with front 98 and back 94 walls. The curved runners optionally have at least one raised rubber runner 102 (better illustrated in FIG. 3 ) positioned at least along a portion of each curved runner 96 , the raised rubber runners on the curved segment of runners 96 softening noise and preventing sliding which would otherwise be created when rocking infant carrier 20 when removed from receiving base 40 . Raised rubber runners 102 on infant carrier 20 are similar to rocking runners common to most infant carriers and are inserted into the shell and formed into an arc underneath the back and seating surfaces. They are spaced apart to allow the molded seat shell center bottom contour to assume an independent shape.
Curved runners 96 have at least one pair of bottom apertures 104 for releasable engagement of a pair of upwardly-extending rearward-facing hooks 128 as described subsequently for releasably securing infant carrier 20 into receiving base 40 . Optionally, a second pair of bottom openings 106 as better shown in FIG. 5 , are present toward the front of curved runners 96 for pivotally securing engagement of left 56 a and right 56 b child lap belt webbing via anchor clips 108 .
Angled back panel 120 of infant carrier is generally recessed at an angle to back walls 94 and further includes rear slot 42 for threading of length adjustment web 52 into clip 112 in threaded communication with left 58 a and right 58 b child restraint shoulder webbing passing through slightly angled slotted openings 116 in child restraint webbing height adjustment means 100 . In a manner to be more fully described in this application, belt height adjustment means 100 is slidably repositionable through cooperation with height adjustment knob 114 through engagement with angled back panel 120 . Toward the top of rear outer plastic shell 88 is recess 118 for releasing the locking engagement of infant carrier 20 from receiving base 40 by upward movement in a manner subsequently described.
FIG. 4 illustrates the interior of outer plastic shell 88 with foam inner liner 92 removed and better illustrates the belt path of length adjustment web 52 after passing through slotted opening 90 in trim bezel 84 (which would be positioned on top of the foam inner liner 92 ). Length adjustment web 52 passes through apertured plastic guide 32 as well as through slotted seat floor guide 30 for egress through rear slot 42 in angled back panel 120 and into secured engagement with clip 112 better illustrated in FIG. 3 . Depressing belt adjustment means 82 permits disengagement thereof with resulting lengthening of length adjustment web 52 and its corresponding lengthening of child shoulder belts 58 a and 58 b through their interconnectivity with clip 112 . Tighter engagement is achieved by the application of an outward force to the end of length adjustment web 52 without the need for depression of belt adjustment means 82 (or equivalently release tab). Alternatively, as illustrated in FIG. 3 b , belt length adjustment may be positioned at the rear of the carrier when rear harness adjustment means 240 is positioned at any applicable location on the rear of outer plastic shell 88 or adjustment panel rear surface 142 .
Left 56 a and right 56 b child lap belts are securely engaged into infant carrier 20 in curved runners 96 by anchor clip 108 pivotably secured in second pair of bottom apertures 106 (better illustrated in FIG. 3 ). Securing engagement is effected into the interior of the carrier base by bracket 26 with slot 28 (better illustrated in FIG. 4 ) providing the pathway for the belt web to pass through side seat slotted child lap belt openings 72 in foam inner liner 92 illustrated in FIG. 2 for connection via either buckle insert 62 a or 62 b into buckle 60 .
The interior side of angled panel 120 has a grid matrix 36 with recesses 38 , at least two recesses 38 are open through outer plastic shell 88 , although preferably at least four through holes 39 will be present as illustrated in FIG. 3 a ) dimensioned for mating engagement with projections 122 on an interior side of belt height adjustment means 100 through sliding movement of height adjustment knob 114 , the projections penetrating into at least one, preferably two or more holes 39 in grid matrix 36 in angled back panel 120 . As better illustrated in FIG. 3 a and FIG. 6 , upward and downward movement of height adjusting means 100 is achieved by overcoming the inward biasing force of spring 136 and the simultaneous application of up or down force by a user with height adjustment knob 114 and engagement block 132 with projections 122 through interconnection via recessed screw attachment 134 . A pair of overlapping securing guides 144 ( FIG. 3 ) are positioned at each lateral extremity of belt height adjustment means 100 , the securing guides configured to permit up and down movement of adjustment means 100 in a channel created between securing guides 144 and the rear surface of outer plastic shell 88 , the channel depth approximating the thickness 146 of belt height adjustment means 100 . Underlying the two hourglass slots 64 in foam inner liner 92 and corresponding hourglass slots 34 in outer plastic shell 88 are two preferably racetrack-shaped slightly inwardly-penetrating and preferably angled belt height positioning means 80 (e.g., slots) which guide and position left 58 a and right 58 b child shoulder belts. The inward penetration of height positioning means 80 is essentially the same as the thickness of the height adjustment panel or less and is better illustrated in FIG. 6 .
Releasable securing engagement of the infant carrier into the receiving base for use as a car seat is achieved by release mechanism means 110 . The mechanism has a recess 118 which is dimensioned to accept at least one (preferably more) fingers of a user when providing an upward force on the mechanism. Extending downwardly and secured to the rear of release mechanism means 110 are a pair of left 124 a and right 124 b arms, (although only one connector is required) each of which preferably terminate in angled slotted openings 220 at a base thereof, the angle measured with respect to the longitudinal axis of arms 124 a and 124 b , the opening dimensioned to preferably accept a cylindrical rod 126 positioned there between. Slotted openings 220 , which may preferably be racetrack-shaped, defines a pathway within which the rod may move in conjunction with supports 46 which extend above the floor of outer plastic housing 88 by pedestal supports 48 and are secured at each end by fastening means 44 such as screws. In the embodiment illustrated in FIG. 6 , rod 126 is biased toward a front of the carrier by rod biasing means 148 , e.g., a spring secured about rod 126 at one end and into the forward fastening means 44 at its opposed end. It is understood by those skilled in the art that the orientation and mechanism of operation of the releasable securing engagement could be reversed using simple engineering principles.
Securing engagement is effected by positioning carrier bottom openings 104 above upwardly-extending rearward-facing hooks 128 affixed to receiving base 40 and allowing penetration of the same into the openings. Upon impingement of rod 126 upon the top of declined surface 150 , the rod will move along the declined surface as well as within the preferred racetrack openings 220 and the gap between pedestal base 48 and rear fastening means 44 . Upon reaching the end of the declined surface, rod 126 will return to its originally biased forward position and seat against the back of slot 68 in upwardly-extending rearward-facing hook 128 . Removal of the carrier from its base involves a reversal of many of the previous steps, and requires upward movement of release mechanism means 110 overcoming the inherent biasing of rod biasing means 148 through the translation of vertical movement into horizontal rearward movement by the cooperation of preferred racetrack opening 220 pulling the rod rearward and thus concomitantly moving rod 126 to the tip of slot 68 in hook 128 , thereby allowing removal of the carrier with resulting return of rod 126 to its original spring-biased position with return of the release mechanism to its original position. Once again, it is understood by those skilled in the art that the rearward-facing hooks could be reversed using simple engineering principles. Preferably hooks 128 and rod 126 are metal, although reinforced plastic is also capable of being used.
Infant carrier 20 has a carrying handle 74 which straddles the carrier. Each leg of the handle is affixed to hubs on the exterior sides of outer plastic shell 88 . The handle is pivotable about an axis for repositioning of the handle between a carrying position as illustrated in FIG. 1 through FIG. 4 and at least one reclined position as illustrated better in FIG. 14 c . As illustrated in FIG. 8 , FIG. 8 a and FIG. 9 , outer plastic shell 88 has a molded hub 78 a and 78 b integrally attached on either side with handle axis 152 having an aligned axis passing there between. These handle hubs are pivotally secured to outer plastic shell 88 on this axis optionally using a fastening means 154 , e.g., a rivet, screw, etc., such that they can rotate to a more-or-less vertical position, a position beyond horizontal to the rear, or any of several other selectable positions between. A series of teeth or gear segments 156 , preferably stamped of metal, but alternatively of strong plastic is secured to or molded into the inside of the hubs on the plastic outer shell. A sliding plate 158 with laterally protruding pin 160 optionally having a protruding pin head 230 secured to the sliding plate preferably by welding such that sliding plate and protruding pin 160 move together in a sliding manner toward or away from the axis 152 of the hub. The protruding pin moves within elongated slot 234 and employs biasing means 162 , e.g., spring, to bias sliding plate 158 away from the hub. Protruding pin 160 is so positioned that it engages gear segment 156 mounted to the shell hub when it is in its outward position as achieved by the spring bias. When protruding pin 160 is engaged in gear segment 156 , rotation of handle 74 is fixed relative to outer plastic shell 88 .
An extension of sliding plate 158 penetrates the outer surface of carry handle hubs 78 a and 78 b and is crowned by plastic push button 164 . Upon depression of push button 164 , sliding plate 158 overcomes the outward bias of biasing means 162 and disengages protruding pin 160 from gear segment 156 . Carry handle 74 rotation relative to plastic shell 88 may then be adjusted. Releasing push button 164 allows biasing means 162 to re-engage protruding pin 160 with gear segment 156 thus re-securing carry handle 74 rotation relative to outer plastic shell 88 . The strength of the handle locking means described above is dependent on at least the strength of the materials selected, the distance of the gear segment from the axis, and the geometry of the gear segment. It is also dependent on the proximity of the sliding plate from the gear segment since at greater distances, protruding pin 160 and sliding plate 158 will tend to twist on the sliding axis. To decrease the tendency of the sliding plate and extending pin to twist on the sliding axis, fixed guide plate 166 is mounted to the inside of the handle hub, sandwiched between gear segment 156 and sliding plate 158 . Fixed guide plate 166 has an elongated slot 234 which allows extending pin 160 to travel inward and outward from the pivot axis, but lessens its tendency to twist about the sliding axis by the presence of elongated slot 234 which permits sliding movement of protruding pin 160 through fixed guide plate 166 as best illustrated in FIG. 8 a . The movement of protruding pin 160 is fixed in sliding plate 158 while axle 152 is permitted to move within elongated slot 236 while correspondingly, protruding pin 160 is permitted to move within guide plate 166 while axle 152 is fixed. Elongated slot 234 resists any tendency of protruding pin 160 to twist. Preferably, both sliding plate 158 and fixed guide plate 166 are made of metal, although once again, reinforced plastic may also be used.
As discussed previously, but now in the context of more fully describing the belt pathways, the seatbelt system consists of a three or five-point harness, consisting of a central buckle 60 from which radiate either: two child shoulder belts ( 58 a and 58 b ) and a crotch strap ( 54 ); or two child shoulder belts ( 58 a and 58 b ), two child lap belts ( 56 a and 56 b ), and a crotch strap ( 54 ). In either case, the shoulder belts pass through hourglass slots 64 in foam inner liner 92 as well as corresponding hourglass slots 34 in plastic outer shell 88 and join either permanently or removably to single length adjustment belt 52 by clip 112 . In the preferred embodiment, length adjustment belt 52 has a sewn loop about one slot in clip 112 . Left 58 a and right 58 b child shoulder belts preferably pass through a second slot in clip 112 , each returning to the front of the car seat by passing through left and right child shoulder belt slots. In the case of a five-point harness, the two shoulder belts pass through the left 62 a and right 62 b buckle inserts and become the left 56 a and right 56 b child lap belts. These lap belt portions of the harness pass through bottom seat surface of seat portion 14 of foam inner liner 92 and slots 28 in outer plastic shell 88 and are secured by belt anchor clips 108 in second pair of openings 106 for engagement with slotted brackets 26 in outer plastic shell 88 .
As better illustrated in FIG. 5 , left and right lap belt anchor clips 108 pivot on a belt anchor axis positioned on one side of the anchor from a position relatively flush with the bottom surface of outer plastic shell 88 to a position protruding from the shell. When the left and right belt anchor clips are in their protruding position, terminating loops 59 of left 56 a and right 56 b lap belts may pass through slots 28 in slotted brackets 26 in outer plastic shell 88 and be placed over the length of belt anchor clips 108 . When the belt anchor clips are again folded to their flush position, the lap belts are secured, they can neither come off of the belt anchor clips, nor can they pass back through the molded shell. This arrangement allows for a single piece lap/shoulder belt which forms both the left and right sides. Anchoring the ends is easy and semi-permanent. The belts can be easily removed for cleaning, but in normal usage are secure.
Length adjustment belt 52 is secured at one end to clip 112 and passes through rear slot 42 in the back of outer plastic shell 88 into a void between the shell and foam inner liner 92 . This adjustment belt continues toward the front of the carrier between the molded seat shell and the foam inner liner until it meets and is adjustably secured by harness length adjustment means 82 mounted to the inside of outer plastic shell 88 and penetrating foam inner liner 92 . The tail of length adjustment belt 52 beyond the adjuster emerges to bottom seating surface 14 of foam inner liner 92 . By means of harness length adjustment means 82 , length adjustment belt 52 can be made either longer or shorter allowing the harness to accommodate various sizes of infants.
Shoulder belt height adjuster means 100 include elongated hourglass slots 34 in outer plastic shell 88 and corresponding hourglass slots 64 in molded foam liner at the point where each shoulder belt passes through them. The slots are of sufficient width to accommodate the shoulder belts and sufficient height so that the belts are free to move from a low position to fit a small infant to a high position to fit a larger infant, or alternatively, any position in-between. The width of each slot may be constricted between the low position and the high position (or intermediate positions if allowed) to minimize the loss of seating surface provided that it is wide enough that each shoulder belt can easily deform and move between the low position and the high position. Adjustment panel 142 is moveably secured to the outside of molded outer plastic shell 88 and is provided with left and right belt height positioning means 80 through which the left and right shoulder belts pass as they travel from the seating side of the foam inner liner to behind the outer plastic shell. Adjustment panel 142 and associated belt height positioning means 80 are allowed to travel so that belt height positioning means 80 travel between the lowest allowable shoulder belt position to the highest shoulder belt position.
The shoulder belts are secured in any of several height positions (in the preferred embodiment, only a low and a high position are illustrated in FIG. 3 a ) by securing adjustment panel 142 to outer plastic shell 88 in any of several corresponding positions. This fastening can be of several means, the preferred being a spring biased engagement block 132 mounted to adjustment panel 142 such that projections 122 on engagement block 132 engage through holes 39 in the outer plastic shell. The spring biased engagement block 132 can be easily disengaged from the molded plastic shell by means of height adjustment knob 114 connected to it by screw attachment 134 and accessible from the back of the outer plastic shell. Moving the shoulder belt height is easy-to-understand and physically intuitive, the operator simply pulls height adjustment knob 114 and moves adjustment panel 142 (and thus the shoulder belts by virtue of their threading into belt height positioning means 80 ) to the desired position. Moving adjustment panel 142 up raises the shoulder belts while moving this panel down lowers the shoulder belts.
As shown in FIG. 10 , receiving base 40 is molded plastic with carrier seat receiving contours which mate with infant carrier 20 as well as with curved runners 96 of the infant carrier. The underside of lower surface 170 rests on an automobile seat. Near one end, the base has an opening on either side ( 172 , 174 ) which allows passage of and retention of an automobile seat belt 176 and a relatively linear path between the two openings so that the automobile seat belt can pass directly from one opening to the other. These two openings and linear path form an automobile belt path.
Although the user can use an automobile seat belt to secure receiving base 40 into an automobile, newer automobiles have special fixed anchorages for children's car seats, and the manufacturers of children's car seats also supply custom belt systems which must be permanently attached to the children's car seats. This system is known as LATCH. The belt path described above also accommodates the LATCH belt system. As shown in FIG. 13 , receiving base 40 has a LATCH belt, or more properly, two LATCH belts 178 a , 178 b . A left LATCH belt 178 a attaches to the belt path near its left end, and a right LATCH belt 178 b attaches to the belt path near its right end. Thus the left and right LATCH belts are independently secured to receiving base 40 and, since their ends are secured, there is no relative movement possible between receiving base 40 and any LATCH belt as would be possible if the LATCH belt were one continuous piece. As shown in FIG. 15 , the LATCH belt ends are stored in storage compartments within receiving base 40 . Each LATCH belt end 224 has a respective storage region 228 in the fixed component 198 . Posts 226 interface with clasps 224 on each LATCH belt for convenient storage thereof in conjunction with LATCH belt adjusters 222 of the LATCH belts.
When an automobile seat belt is used to secure the base in an automobile the automobile seat belt 176 is routed across the belt path from one opening 172 to the other 174 and secured. If an automobile seat belt with a shoulder belt is used, both are passed across the belt path. Slack is then worked out of the automobile seat belt and it is made as tight as possible and thus secures the base as securely as possible to the automobile seat. As shown in FIG. 12 , the base is provided with lock-off 180 located in the belt path to more firmly secure the automobile seat belt to the base and help prevent any sideward relative sliding between the base and the automobile seat belt. The lock-off further aids in securing the base when the automobile lap/shoulder belt has a free-sliding latch plate and an emergency locking shoulder belt by clamping the lap and shoulder belts together and minimizing potential movement between them. Lock-off 180 comprises a transverse groove 202 in receiving base 40 in the central part of the belt path. A raised rib 182 with a knurl 184 is positioned in the center of transverse groove 202 . Hollow channel lock-off beam 186 is pivotally attached to receiving base 40 at one end of transverse groove 202 through apertured openings in beam channel 186 through which is inserted pivot pin 204 captured within pivot housing 206 and can pivot from an open position ( FIG. 12 ) to a closed position ( FIG. 10 ) where it is essentially parallel to the transverse groove.
As shown in FIG. 11 , lock-off beam 186 can be secured in the second, essentially parallel position by any of several means, the preferable being spring-biased 194 plunger 196 on its free end whereby the spring-biased plunger has a protruding lip 188 which can engage a similar reversed lip 190 in the base. Lock-off beam is provided with left extending wall 192 a and right extending wall 192 b which fall in transverse groove 202 in receiving base 40 on either side of knurled 184 rib 182 in the transverse groove. When the automobile seat belt (or seat belt and combined shoulder belt) are captured between transverse groove 202 with knurled 184 rib 182 and the extending walls ( 192 a , 192 b ) of lock-off beam 186 , they are forced into a “W” form and pushed into the knurled rib thus greatly diminishing the ability of the seat belt(s) to move relative to receiving base 40 .
Lower surface 170 of receiving base 40 is divided into two parts, one of which is fixed 198 , the other which is movably attached 200 to the base so that it can control the angle of the base relative to horizontal, thus changing the angle of the infant carrier and the infant's seating angle. In the preferred embodiment, fixed base component 198 is secured to the bottom of receiving base 40 and movable base component 200 , in the form of a front foot, protrudes from an opening in the front of fixed base component 198 and is guided by any of several means on a vertical axis within a defined range of travel. The more front foot 200 protrudes, the more reclined the seating angle.
Angular control of the movable panel is achieved by turning knob 208 on threaded rod 210 running the length of receiving base 40 and rotatably attached to the base. Turning knob 208 moves a matingly threaded follower 212 on threaded portion 214 of rod 210 . Lateral extensions 216 (of which only one is shown in FIG. 14 a ) on follower 212 drive against inclined track 218 a or 218 b , the top portion of 218 b being removed for purposes of illustration in FIG. 14 a , on front movable base component 200 driving the movable base component out of telescoping opening 242 if the knob is turned one direction and in if the knob is turned in the opposed direction. Knob 208 is accessible at all times and adjustment can be affected with infant carrier 20 on receiving base 40 or not on the base. Access is continuously available without removing or unfastening the automobile seat belt or LATCH belt.
As better illustrated in FIG. 14 b and FIG. 14 c , infant carrier/car seat combination 10 is positioned into rear vehicle seats 244 in a manner which reverses the designations of front and rear discussed in this application. The front of combination 10 is placed toward the rear of the car seat, thereby allowing a user complete access to belt height adjustment means 100 , release means 110 and base height adjustment knob 208 which as discussed previously, are positioned at a rear of carrier 20 , but are now facing toward the front of an automobile. In addition, belt length adjustment is also accessible to a user in that belt length adjustment web protrudes from the carrier from a top surface thereof.
In an alternate embodiment, fixed base component 198 is permanently attached to the rear of the base and has a bottom contour which is somewhat concave in the middle so that it will not rock on a contoured automobile seat. Moveable base component 200 is attached to the base on a transverse axis near the bottom of the base and near the center of the base length, and can pivot on that axis within a defined angle. Links attached to the follower and the movable panel changes the angle of the moveable panel as the knob is turned and the follower moves.
While the invention has been described with reference to the combination of an infant carrier 20 positioned in a receiving base 40 , there is no need to limit the invention to such. In fact, what is important is that the receiving base have at least one upwardly extending essentially J-shaped hook for releasably securing engagement therewith. In one embodiment of this invention, receiving base 40 is substituted with carriage stroller 250 which as illustrated in FIG. 16 , has a pair of upwardly-extending forward-facing J-shaped hooks 246 for insertion into corresponding openings 104 in rocker base 96 of carrier 20 (not shown). J-shaped hooks 246 are dimensioned such that downward positioning of infant carrier toward floor 248 will effect engagement of rod 126 into slotted openings of the hooks in a manner analogous to that described previously with respect to FIG. 6 .
This invention has been described in detail with reference to specific embodiments thereof, including the respective best modes for carrying out each embodiment. In the foregoing description, certain terms have been used for brevity, clearness and understanding; but no unnecessary limitations are to be implied there from beyond the requirements of the prior art, because such terms are used for descriptive purposes and are intended to be broadly construed.
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An infant carrier and car seat combination is illustrated which provides releasable lockability between the carrier and its base, infant seat belt tensioning and height adjustment, improved handle movement which resists twisting and carrier base adjustment through a movable base within the carrier base.
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FIELD OF THE INVENTION
This invention relates to an optical device module for housing optical transmitters and receivers. Preferably the module is designed to enable optical devices to be easily inserted into and removed from modular equipment racks.
DISCUSSION OF THE BACKGROUND ART
Conventionally, optical devices have not been designed for use in modular systems. Therefore such optical devices are housed in a conventional manner in a housing which is designed to remain in one location, and which provides suitable electromagnetic shielding to prevent emissions from an optical device interfering with external devices and equipment.
However, a requirement for flexible modular optical equipment introduces a requirement for an optical device module which provides the required electromagnetic shielding capability for modules which may be inserted and removed from modular equipment racks. Since during normal operation the modules may reach temperatures of up to 85 degrees centigrade, the module should provide adequate thermal insulation as well as electromagnetic shielding so that modules may be inserted and removed without powering down the equipment rack, and waiting for the module to be removed to cool down.
It will be appreciated that the above requirements are conflicting because electromagnetic shielding is usually provided using a material which is electrically conductive, which in general, means that the material is also thermally conductive. So the required thermal insulation will not be achieved.
SUMMARY OF THE INVENTION
According to the present invention there is provided an optical device module comprising a case for housing an optical device and a plastic flange having means for receiving an optical connector, in which the plastic flange has been coated with a metal coating and is connected to the case so that the optical device is substantially enclosed.
Electromagnetic emission may be reduced further if the module further comprises an electromagnetic shielding gasket arranged between the case and the flange. Preferably the gasket is compressed between the flange and a panel of a modular equipment rack when the module is received by the modular equipment rack.
In one embodiment the flange is connected to the case by means of a snap fitting and in a second embodiment the flange is connected to the case by means of a screw.
For improved heat dissipation, preferably the case is fabricated from metal and has fins for heat dissipation.
In a preferred embodiment the metal coating comprises a layer of copper coated with a layer of nickel.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention will now be described, by way of example only, with reference to the accompanying drawings, in which
FIG. 1 illustrates a modular optical equipment rack;
FIG. 2 illustrates the modular optical equipment rack of FIG. 1 with an optical module partially inserted;
FIG. 3 illustrates a first embodiment of an optical module;
FIG. 4 illustrates a second embodiment of an optical module;
FIG. 5 illustrates a view of part of the embodiment illustrated in FIG. 4 , and
FIG. 6 illustrates a second configuration of parts illustrated in FIG. 4 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1 , a modular optical equipment rack 1 comprises a plurality of apertures 2 in a front panel 14 for receiving optical modules 3 . These optical modules 3 may be modules containing one or more optical devices such as optical transmitters and receivers.
An optical transmitter receives an electrical signal via an electrical connector at the rear of the module within the modular equipment rack 1 and converts the electrical signal into an optical digital signal which is then transmitted via a light source to an optical fibre which is connected to the module 3 via an optical connector inserted into an aperture in the module 3 .
An optical receiver receives an optical signal from an optical fibre connected to the module 3 via an optical connector inserted into an aperture in the module 3 . The optical signal is received via a light sensitive element and converted into an electrical signal which is then sent via an electrical connector at the rear of the module 3 within the modular equipment rack 1 to electrical devices as required.
A module 3 often contains an optical transmitter and an optical receiver to form a transceiver pair.
In general the means for receiving the optical connector is provided by an aperture in the front face of the module, however the optical connector may be received by any conveniently shaped space in the module housing.
Use of a modular optical equipment rack as described above allows a customer to have much more flexibility than use of non modular system; the customer can have as many or as few optical transmitters or receivers as required. Furthermore, the equipment can start with a few modules, and more modules may be added, as more capacity is required.
In optical devices the frequency of the signal may be up to 40 GHz. In non modular systems shielding the devices so that they do not generate electromagnetic interference (EMI) is conventionally done by housing the components in a metal box so that the devices are shielded. However a more complex housing is now required, as the module has to be manufactured to slot into to a modular equipment rack 1 and furthermore must be removable at high temperatures generated during operation of the devices housed within.
FIG. 2 illustrates a view of a module 3 according to the invention which is partially inserted into a modular equipment rack 1 . The module 3 has two apertures 4 , 4 ′ in a front panel 5 which is referred to as a flange in the following description. The flange 5 receives an optical connector for a transmitter and an optical connector for a receiver housed in the module 3 . The module 3 is attached to the modular equipment rack 1 using a pair of thumbscrews, of which one thumbscrew 6 in shown.
FIG. 3 is a more detailed view of a module 3 according to the invention. A metal case 7 houses an optical transmitter and an optical receiver. The metal case 7 has a plurality of fins 8 disposed along the top of the case to aid heat dissipation. It can be seen that the flange 5 is a fairly complex shape, and is manufactured from a plastic material, which allows more flexibility in design than a metal material. A plastic flange may incorporate more intricate features and the tolerances for manufacturing using plastic may be much finer. Using plastic also reduces manufacturing cost as the tooling costs are much lower.
The plastic flange is not thermally conductive so it is possible to remove and insert optical modules from the modular equipment rack without having to power down the equipment, as the front panel is thermally insulated from the case housing the optical devices.
In order for the module to have the required EMI shielding the flange 5 is metalised, using a conventional process. The plastic flange is dipped into acid, which forms micro cavities on the surface of the plastic to allow for adhesion of electroless copper to the surface. Then electrolytic nickel is deposited onto the copper using a conventional electroplating process. For sufficient EMI shielding it has been found that a metal coating comprising 1-3 mm copper and 0.5 mm nickel is sufficient, although thicker or further layers could optionally be applied. The thickness of the coating is such that the flange does not become excessively thermally conductive. Other metals which may be used include chrome or gold amongst others.
Referring still to FIG. 3 , there is shown an EMI gasket 9 . When devices operate at high frequency (i.e. the wavelength is small) then any slots or gaps in the module will cause the EMI shielding to be reduced. The EMI gasket 7 helps to alleviate this problem by providing a conductive medium to provide a continuous low impedance joint between the flange 5 and the casing 7 . The EMI gasket may be manufactured from a conductive elastomer.
In the embodiment of the invention shown in FIGS. 2 and 3 the gasket 9 is compressed between the flange 5 and the front panel 14 by means of the thumbscrews.
A second embodiment of the invention is illustrated in FIGS. 4 , 5 and 6 , in which similar parts are labelled with similar numerals marked with a prime.
Referring now to FIG. 4 , an optical module 3 ′ comprises a case 7 ′ having a plurality of fins 8 ′ for housing an optical transmitter. A flange 5 ′ fabricated from a metalised plastic as described above is connected to the case 7 ′ via an EMI gasket 9 ′. Hooked legs 11 protruding from the flange 5 ′ are used to secure the flange 5 ′ to the case 7 ′.
FIG. 5 is a perspective view from the top of the module illustrated in FIG. 4 in which the top of the case 7 ′ has been removed to show a bottom part 12 of the case 7 ′. Here corresponding hooks 13 are shown which locate the hooked legs 11 when the flange 5 ′ and the case 7 ′ are pushed together, this forming a snap fit which serves to compress the gasket 9 ′. This embodiment illustrates another advantage of the plastic flange, as it is much simpler to fabricate the flexible hooked legs 11 from a plastic material rather than a metal based one.
FIG. 6 illustrates the module of FIG. 5 when assembled, again with a top part of the case 7 ′ removed in order to view the bottom part 12 .
Provision of a detachable flange 5 ′ provides a further advantage for the manufacturer because the same case 7 ′ may be provided to customers who require a modular system as described above, and to customers who require a conventional non-modular system with fixed components.
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An optical device module for housing optical transmitters and receivers. Preferably, the module is designed to enable optical devices to be easily inserted into and removed from modular equipment racks. The module comprises a case for housing an optical device and a plastic panel having an aperture for receiving an optical connector, in which the plastic panel has been coated with a metal coating and is connected to the case so that the optical device is substantially enclosed.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention pertains to a process for the preparation of 1,1,1,2-tetrafluoroethane (HFC-134a). In particular it pertains to a process for the preparation of HFC-134a by a vapor phase catalyzed fluorination of 1,1,1-trifluoro-2-chloroethane (HCFC-133a) with hydrogen fluoride in a first reactor and flowing the resulting product to a second reactor together with trichloroethylene (TCE) and hydrogen fluoride (HF). The second reaction is conducted in the presence of a fluorination catalyst at a higher temperature than the first reaction.
2. Description of the Prior Art
It is known in the art that HFC-134a is a useful compound as a replacement for environmentally disadvantageous chlorofluorocarbon refrigerants. It is also useful as a blowing agent and as an aerosol propellant. Many methods for the production of HFC-134a are known in the art. U.S. Pat. Nos. 5,243,105 and 5,395,996 disclose a method of producing HFC-134a by a two step process which reacts trichloroethylene with hydrogen fluoride to form HCFC-133a. The HCFC-133a is then reacted with hydrogen fluoride in a second reaction to form HFC-134a. In these disclosures, the reaction of trichloroethylene with hydrogen fluoride to form HCFC-133a must be conducted at a lower temperature than the reaction of HCFC-133a with hydrogen fluoride. The reaction sequence and temperature differences are the reverse of those used in the present invention. U.S. Pat. Nos. 5,243,107 and 5,382,722 disclose the reaction of HCFC-133a and HF in a first reaction zone and then passes the reaction product to a second reaction zone together with trichlorethylene. This second reaction zone is at a lower temperature than the first reaction zone. Again, this is the opposite to the temperature difference sequence of the present invention. U.S. Pat. Nos. 5,334,786 and 5,395,998 produce HFC-134a by reacting trichloroethylene and hydrogen fluoride to produce HCFC-133a and then further fluorinate the HCFC-133a. The latter process requires a dilution of the trichloroethylene and hydrogen fluoride with nitrogen or argon gas which is inert to the reaction, and also requires three reactors for this process. U.S. Pat. No. 4,158,675 prepares 1,1,1,2-tetrafluoroethane HFC-134a by a vapor phase catalyzed fluorination of HCFC-133a with hydrogen fluoride in a first reactor. The reaction conditions produce unwanted 1,1-difluoro-2-chloroethylene as an impurity which is reacted with hydrogen fluoride.
It has been a problem in the art to achieve relatively high yields of HFC-134a without causing the simultaneous production of inordinate amounts of by-products which must be treated and disposed of safely. The present invention employs a method wherein intermediate mixtures are recycled through the production steps, thus increasing the efficiency of the process. The higher reactor temperature for the second reaction step affords several advantages. These include higher HCFC-133a productivity and higher TCE conversion. Therefore one can use a smaller reactor and less catalyst. Consequently, operating costs and capital investment are reduced. High conversions of trichloroethylene, approaching 100%, are made possible. Higher TCE conversion can eliminate the possibility of phase separation in the recycle stream. It also reduces amounts of TCE fed to the first reactor, which helps reduce the generation of HCl in the first reactor, and thus raises the equilibrium amounts of HFC-134a product formed in the first reactor. The amount of hydrochlorofluorocarbons as by-products is substantially reduced or eliminated. The process also produces useful HFC-125 and HFC-143a by-products instead of HCFC-123/124 and HCFC-141b/142b, respectively. The HFC-125 and HFC-143a, which are also useful refrigerants, have no ozone-depleting potential whereas HCFC-123/124 and 141b/142b have ozone-depleting potential and are being phased out. Energy is saved because refrigeration is not required to separate crude HFC-134a product from HCFC-133a and hydrogen fluoride that are recycled to the first reactor. In addition, since the reaction of trichloroethylene and hydrogen fluoride is exothermic, heat generated from this reaction is used to keep the second reactor at a higher temperature.
SUMMARY OF THE INVENTION
The invention provides a process for the preparation of 1,1,1,2-tetrafluoroethane which comprises:
a.) conducting a first reaction step comprising vaporizing a first recycled composition comprising hydrogen fluoride and 1,1,1-trifluoro-2-chloroethane at a hydrogen fluoride to 1,1,1-trifluoro-2-chloroethane mole ratio of at least about 1:1, and reacting the composition under suitable conditions in the presence of a fluorination catalyst to thereby form a first reaction product mixture comprising 1,1,1,2-tetrafluoroethane; and
b.) conducting a second reaction step comprising vaporizing a second composition comprising hydrogen fluoride, trichloroethylene and the first reaction product mixture from step (a) such that the mole ratio of hydrogen fluoride to trichloroethylene is at least about 3:1 and wherein the second reaction step is conducted in the presence of a fluorination catalyst and at a temperature which is higher than the first reaction step, to thereby form a second reaction product mixture comprising 1,1,1,2-tetrafluoroethane, 1,1,1-trifluoro-2-chloroethane, hydrogen fluoride, trichloroethylene and hydrogen chloride.
In the preferred embodiment, one subsequently recovers 1,1,1,2-tetrafluoroethane. This may be done with the ensuing steps of:
c.) recovering hydrogen chloride by a first distillation from the second reaction product mixture product of step (b);
d.) recovering a product comprising 1,1,1,2-tetrafluoroethane by a second distillation from the mixture resulting from step (c), and obtaining a recycling mixture of 1,1,1-trifluoro-2-chloroethane, trichloroethylene and hydrogen fluoride from the second distillation and adding the recycling mixture as a feed to step (a); and
e.) recovering substantially pure 1,1,1,2-tetrafluoroethane from the product of step (d).
Another embodiment of the invention provides optionally adding a portion of the recycling mixture of 1,1,1-trifluoro-2-chloroethane, trichloroethylene and hydrogen fluoride from the second distillation as a feed to the second reaction step (b). Still another embodiment of separating HCl from the first reaction product mixture of the first reactor.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows a schematic representation of an equipment arrangement suitable for the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The first step (a) in the production of HFC-134a is vaporizing and reacting a first recycled composition comprising hydrogen fluoride and HCFC-133a in a first reactor. This reactor is shown as R1 in FIG. 1. While fresh hydrogen fluoride and HCFC-133a may be employed here, the process contemplates the composition to contain recycled material from step (b) as hereinafter described. The mole ratio of hydrogen fluoride to HCFC-133a is adjusted to be at least about 1:1, preferably from about 1:1 to about 100:1, more preferably from about 2:1 to about 80:1, and most preferably from about 3:1 to about 60:1. Mole ratios of greater than about 100:1 can be used, however such are less economical. The vaporized composition is preferably heated to a temperature of from about 250° C. to about 425° C., more preferably from about 280° C. to about 400° C. and most preferably from about 300° C. to about 375° C. in the first reactor. The reactor temperature is measured at its outlet end. The pressure of the reactor is not critical. Operating pressure is preferably between about 0 to about 200 psig and still, preferably, from about 50 to about 150 psig. The first reactor is preferably an adiabatic reactor filled with a fluorination catalyst. The organic vapor is allowed to contact the fluorination catalyst for from about 1 to about 100 seconds or more preferably from about 3 to about 70 seconds and most preferably from about 5 to about 60 seconds. For purposes of this invention, contact time is the time required for the gaseous reactants to pass through the catalyst bed assuming that the catalyst bed is 100% void. Any of the fluorination catalysts known in the art may be used. Such fluorination catalysts non-exclusively include chromium, aluminum, cobalt, manganese, nickel and iron oxides, hydroxides, halides, oxyhalides and inorganic salts thereof, Cr 2 O 3 /Al 2 O 3 , Cr 2 O 3 /AlF 3 , Cr 2 O 3 /carbon, CoCl 2 /Cr 2 O 3 /Al 2 O 3 , NiCl 2 /Cr 2 O 3 /Al 2 O 3 , CoCl 2 /AlF 3 and NiCl 2 /AlF 3 . Chromium oxide/aluminum oxide catalysts are described in U.S. Pat. No. 5,155,082 which is incorporated herein by reference. The chromium oxide may be crystalline chromium oxide or amorphous chromium oxide. Amorphous chromium oxide is preferred. Chromium oxide (Cr 2 O 3 ) is a commercially available material which may be purchased in a variety of particle sizes. The catalyst is present in the amount necessary to drive the reaction. In the preferred embodiment, small amount of gaseous oxygen or air flows through the chromium oxide to maintain catalyst activity. The amount of air or oxygen supplied to the reactor is preferably from about 0.01 to about 30 mole percent of oxygen relative to the total organics fed to the reactor. A more preferred amount ranges from about 0.05 to about 20 mole percent and most preferably from about 0.1 to about 10 mole percent. The resultant reaction mixture comprises HFC-134a, HCFC-133a, hydrogen fluoride, HCl and small amounts of other by-products.
Step (b) is preferably conducted simultaneously with step (a) and includes vaporizing a second composition comprising hydrogen fluoride, TCE and the first reaction product mixture resulting from step (a) which has been allowed to flow from the first reactor R1 along line 1 to the second reactor R2 as shown in FIG. 1. The HF, TCE and first reaction product mixture resulting from step (a) combine and flow along line 5 to reactor R2 as shown FIG. 1. The process contemplates the composition reacted in step (b) to contain a fresh supply of TCE and HF and optionally recycled material from step (d) as hereinafter described. This second composition is heated to a temperature of about 255° C. to about 430° C., or more preferably from about 285° C. to about 405° C. and most preferably from about 305° C. to about 380° C. Again, the reactor temperature is measured at its outlet end. It is an important feature of the invention that the second reaction step (b) be conducted at a temperature which is higher than that of the first reaction step (a). In the preferred embodiment, the temperature difference between step (a) and step (b) ranges from about 5° C. to about 130° C., or more preferably from about 5° C. to about 60° C. and most preferably from about 5° C. to about 30° C. The pressure of the reactor is not critical. Operating pressure is preferably between about 0 to about 200 psig and still, preferably, from about 50 to about 150 psig. The second reaction step is also conducted in the presence of a fluorination catalyst which may be any of those enumerated as being suitable for the first reaction step (a). The contact time in the second reaction step (b) also may be in the range mentioned above as being suitable for the first reaction step (a). In the second reaction step (b), the reacted mole ratio of HF to TCE may range from about 3:1 to about 100:1, or preferably from about 4:1 to about 90:1 and more preferably from about 5:1 to about 80:1. Mole ratios above 100:1 may be used but are less economical. While the first reaction product mixture is passed to the second reactor in step (b), 1,1,1,2-tetrafluoroethane is made mainly in the first reaction. It then passes through the second reactor. It is contemplated that the non-HFC-134a by-products of the first reaction product mixture may take part in the second reaction. The second reaction product mixture principally produces HCFC-133a and it, together with untreated HF are recycled back to the first reactor where HFC-134a is produced. In the preferred embodiment, for both reaction steps (a) and (b), process flow is in the down direction through the bed of the catalyst. The catalyst is preferably pre-treated and activated as well as regenerated after prolonged use while in place in the reactor. Pre-treatment can be done by heating the catalyst to about 250° C. to about 430° C. in a stream of nitrogen or other inert gas. The catalyst is then activated by treating with a stream of HF diluted with nitrogen gas in order to obtain high catalyst activity. Oxygen is preferably continuously fed to each reactor during production to maintain catalyst activity. Oxygen is fed at a rate sufficient to provide an oxygen to organics mole ratio of from about 0 to about 0.1 or preferably from about 0.005 to about 0.05. If the catalyst is de-activated, it can be regenerated by heating to about 250° C. to about 430° C. in a stream of nitrogen containing a low concentration of oxygen, followed by cooling. Each of the reaction steps (a) and (b) may be conducted in any suitable reaction vessel but it should be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride such as Hastalloy, Inconel and Monel.
The next step (c) in the process recovers hydrogen chloride by a first distillation from the second reaction product mixture product of step (b). The second reaction product mixture flows along line 6 and is subjected to such a distillation by column C1 as shown in FIG. 1, to form a distillate portion and a bottoms portion. The purpose of the distillation is to separate hydrogen chloride from the balance of the second reaction product mixture components. This is done using a standard distillation column in a method well known to one skilled in the art. The distillation is preferably conducted at a pressure which ranges from about 5 psig to about 500 psig, preferably from about 10 to about 400 psig and most preferably from about 50 to about 300 psig. The pressure of the distillation column inherently determines the distillation operating temperature. The distillate portion includes substantially all the hydrogen chloride and the bottoms portion includes the balance of the second reaction product mixture components. The bottoms is then subjected to a second distillation by exiting line 7 and flowing to column C2 as shown in FIG. 1.
Step (d) requires recovering a product of step (c) comprising HFC-134a also by a standard distillation column in a method well known to one skilled in the art such as listed above to form a distillate and a bottoms mixture. The distillate comprises substantially all of the HFC-134a product plus other useful hydrofluorocarbon by-products such as HFC-125 and HFC-143a. The HCFC-133a, hydrogen fluoride and TCE bottoms mixture is recycled back to step (a) as shown by the recycle line of FIG. 1. Step (e) recovers a composition comprising substantially pure HFC134a from the product of step (d) and the other useful hydrofluorocarbon by-products such as HFC-125 and HFC-143a. This is done by standard distillation or other known separation techniques.
The following non-limiting examples are prospective and represent standard process simulation and physical property prediction procedures and the examples serve to illustrate the invention.
EXAMPLES 1-3
These examples demonstrate the effect of temperature on productivity and conversion. In three different experiments, a TCE and HCFC-133a mixture was fed to a packed bed, isothermal reactor at 260° C., 320° C., and 360° C., respectively. The reactor was packed with chrome oxide catalyst. The mole ratio of HCFC-133a to TCE was about 3.3. HF was fed in separately. The mole ratio of HF to TCE was about 13. Air was co-fed at 1.4 mole % O 2 /organics mole ratio. Reactor pressure was 200 psig. Organics and HF feed rates were adjusted to give the desired contact times of 20, 10, and 5 seconds, respectively. The results are listed below:
TABLE I______________________________________ Contact ProductivityTemp. Time (%) TCE (lbs/hr/ft.sup.3)Example °C. seconds Conversion HCFC-133a HFC143a______________________________________1 260 20 54.9 17.8 <0.12 320 10 59.8 23.9 3.43 360 5 99.5 80 15______________________________________
Example 3 is calculated using a reaction kinetic model which was derived from experimental data. These data show the higher the reaction temperature of the second reactor, the higher the TCE conversion, and the higher the HCFC-133a productivities.
EXAMPLES 4, 5 and COMPARATIVE EXAMPLE 6
These examples are to demonstrate the effect of higher temperature in the second reactor on TCE conversion, 133a productivity and useful by-product formation using an integrated system shown in FIG. 1. Examples 4 and 5 were conducted in adiabatic reactors packed with chrome oxide catalyst. TCE and HF were fed to the second reactor (R2) as shown in FIG. 1. HCl is taken off from the HCl column and the heavy cut, consisting of 134a/HF/TCE/133a and other by-products were fed to the crude 134a distillation column where 134a/125/143a/124 were taken off and 133a/HF/TCE were recycled to the first reactor as indicated in FIG. 1. The reaction conditions and parameters are listed in Table 2, with TCE conversion, 133a productivity and amounts of useful by-product formation:
TABLE 2______________________________________Example 4 5 Comp. 6______________________________________R1 outlet temperature (°C.) 329 333 350R2 outlet temperature (°C.) 341 361 260Pressure (psig) 60 60 60Contact Time in R1 (seconds) 9 9 9Contact Time in R1 (seconds) 9 9 9HF/133a mole ratio in R1 14 14 14HF/133a mole ratio in R2 12 12 12HF/TCE mole ratio in R2 43 43 58TCE conversion in R2 (mole %) >99% >99% 29%133a productivity in R2 (lbs/hr/ft.sup.3) 7 7 1.4Useful by-products:wt % HFC-125 in HFC-134a 0.11 0.89 --wt % HFC-143 in HFC-134a 0.007 0.16 --Recycle composition(wt % major components)HF 65% 65% 70%TCE <0.1% <0.1% <6%133a 33% 31% 23%______________________________________
Data of comparative Example 6 are generated for comparable conditions using computer simulation which was derived based on numerous experimental and production data. As indicated in the present invention and shown in the above examples, higher TCE conversion, and higher 133a productivity were obtained when the second reactor (R2) was run at a higher temperature than the first reactor (R1). The TCE concentration was about 0 in the recycle, compared to 6% (about 19% based on total organics). Useful HFC by-product formation was also evident.
EXAMPLE 7
This example demonstrates the energy savings for separating HCl before recovering crude HFC-134a from HCFC-133a and HF that is recycled to the first reactor.
The condensing equipment of the recycle column used to separate the crude HFC134a from the HCFC-133a and HF recycle to the reactor was calculated using a distillation model derived from theory and laboratory measurements of component vapor-liquid equilibrium. The calculation showed that when the HCl co-produced in the reaction is removed together with HFC-134a in the recycle column, the condensing temperature is very low so that refrigeration is required to produce reflux in this column. However, when the HCl is removed first, according to the present invention, the need for refrigeration to produce reflux in the recycle column can be eliminated, thus saving the capital cost of the refrigeration system as well as the cost of energy to operate it. An additional operating energy cost of about 350 HP per metric ton of HFC-134a product are required when HFC-134a and HCL are separated together from HCFC-133a and HF at a normal operating pressure of 150 psig. No refrigeration is required in the recycle column when the HCl is removed first. The energy savings are even greater if the reactors are operated at lower pressure.
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This invention relates to a process for producing 1,1,1,2-tetrafluoroethane (HFC-134a). The process reacts, 1,1,1-trifluoro-2-chloroethane (HCFC-133a) and hydrogen fluoride in a first reactor. The product resulting from the first reaction step is brought to a second reactor together with trichloroethylene and hydrogen fluoride. The second reaction is conducted at a higher temperature than the first reactor. Optionally, HCl is removed prior to removal of the crude HFC-134a product. Unreacted HCFC-133a, trichloroethylene and hydrogen fluoride may be recycled back to the first reactor.
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BACKGROUND OF THE INVENTION
This invention relates generally to air inflatable structures and more specifically relates to air inflatable structures incorporating means to limit the heat flow into and out of the space thereby enclosed.
In recent years, a variety of causes have combined to provide a very high order of interest in so-called air-inflated structures. These structures are essentially a flexible shell, formed, for example, of tough plastic material, such as for example, a nylon or dacron cloth impregnated with a vinyl or vinyl residue, which shell is maintained in an inflated, expanded condition by a positive air pressure, supplied within the space thereby covered, as for example by simple air-pumping means. In part, the said structures have become practical, and, therefore, increasingly used, because of the development of the type of plastic materials which lend themselves to the structures represented. However, there are more basic causes for the increased popularity of the structures, such as for example, the ever-increasing cost of constructing permanent frame buildings, and the fact that structures of the inflatable type may be set up and put to work performing their function within a matter of hours as opposed to weeks or months, as is the case with more permanent structures. The inflatable structures have moreover become of increasing interest because of their ready adaptability to use in enclosing recreational facilities, such as for example tennis courts and swimming pools. Such recreational facilities have come into increasing and more widespread use within recent years and a consequent increase in interest has occurred with respect to coverings enabling use of such recreational facilities on a year-round basis.
In this latter connection, it may be noted that one of the most significant shortcomings presently limiting what would otherwise be an even more wide-spread use of inflatable structures, is the fact that such structures are notoriously ineffective in restraining heat transmission into and out of the thus enclosed space. This unfortunate occurrence is basically due to the fact that a space enclosed by the said structures is separated from the ambient environment only by the thin wall of the inflated structure. The consequent, inordinately high heat transmission co-efficient for the stucture, makes the heating and air-conditioning of the enclosed space both difficult and very expensive. Troublesome condensation also arises when the moist, warm interior air contacts the cold, thin wall of the air structure. These factors negate much, if not all, of the economic advantages of utilizing such a structure in those many cases where heating or air-conditioning is a requirement.
In accordance with the foregoing, it may be regarded as an object of the present invention to provide air-inflated structures wherein the heat transmission through the walls thereof is so severely diminished that the structures may be economically heated and air-conditioned.
It is another object of this invention to provide air-inflated structures wherein the tendency for moisture condensation upon the walls thereof is so severely diminished that a comfortable environment is provided within the structure.
It is a further object of the present invention to provide air-inflated structures which include means for insulating the walls thereof against heat flow into and out of the enclosed space, which insulating means are provided in a simple and inexpensive manner and by the addition of relatively little weight to the basic structure.
It is a still further object of the present invention to provide a construction for insulating air-inflatable structures, which is particularly adaptable to the sculptured type inflatable structures utilizing shroud lines, and which when incorporated into such structures provides a highly effective and low-cost insulation against heat transmission into and out of the enclosed space.
It is yet an additional object of the present invention, to provide a construction for insulating the walls of inflatable structures, which readily lends itself to mass production techniques and which adds little cost and very little weight to the walls of such inflatable buildings.
SUMMARY OF INVENTION
Now in accordance with the present invention, the foregoing objects, and others as will become apparent in the course of the ensuing specification, are achieved through use of thin plastic films so secured to the inner walls of the inflatable structures as to provide one or more thin layers of dead air space between the walls and the enclosed space. The thin plastic films are secured to the boundaries of the basic surface geometries comprising the shell walls and are joined to the shell wall at locations within the boundaries of its curved surface geometries by direct attachment or via flexible anchor tie strips, whereby in its inflated state the outer shell wall extends the film in relatively taut fashion across its curved surface geometries to define a thin, uniform and dimensionally stable insulating air space between wall and film. Plural sets of plastic film, spaced approximately parallel, may be utilized to further curtail the said heat flow by thus providing a plurality of thin insulating air spaces.
BRIEF DESCRIPTION OF DRAWINGS
The invention is diagrammatically illustrated, by way of example, in the drawings appended hereto in which:
FIG. 1 is a schematic diagram illustrating the basic principles of the present invention as applied to a cylindrically shaped portion of an inflatable structure.
FIGS. 2 and 2a are schematic diagrams similar to FIG. 1, setting forth the principles of the invention as applied to part of a spherically shaped inflated structure.
FIG. 3 is an isometric depiction of a sculptured structure with which the present invention may be employed.
FIG. 4 is a fragmentary partially sectional view through the wall of the FIG. 3 structure, taken along the line 4-4' and illustrates arrangement of the components utilized in the invention.
FIG. 5 is a cross-sectional view through a wall structure similar to FIG. 4, but incorporating a plurality of insulating thin films; and
FIG. 6 illustrates an embodiment of the invention wherein distinct anchor tie elements are not used.
DESCRIPTION OF PREFERRED EMBODIMENT
In FIG. 1, a diagram appears illustrating the basic principles of the present invention as applied to a cylindrically shaped portion of an inflatable structure. In connection with this figure, it should be appreciated that the showing is highly schematic in nature and is not intended to depict details of the structure, which will rather appear and be further described herein below.
In FIG. 1, a generally cylindrically shaped concave section 11 of an inflatable structure is set forth. Section 11 may be regarded as a comparatively large portion of an inflated structure, as for example the arched roof of an inflatable structure enclosing a tennis court or the like; or alternatively, the section 11 may be considered as merely representing a small element of an inflated structure, as for example, a billowing section defined between a pair of shroud lines which might thus be present at the edges 15 and 17 of the section. Section 11, in any event, is in its inflated, expanded condition, with the skin 13 displaced to its fully expanded state by positive air pressure provided within the space 19. The skin 13, even as apparent in the present schematic showing, comprises a single layer of tough, flexible cloth-like material, typically a nylon or dacron cloth impregnated with vinyl or a vinyl residue.
In accordance with the principles of the present invention, a thin plastic film 21 is secured to the edges 15 and 17 of section 11. Thus, specifically, the film 21 which is typically a continuous film of polyvinyl chloride or similar thermoplastic material, and has a thickness typically of the order of 2 mils, is secured, as for example, by heat sealing to skin 13 along the edges 15 and 17. The width of film 21 of section 11 extending between edges 15 and 17 is of shorter dimension than the width of the skin 13 of section 11. The film 21 is secured to skin 13 at locations intermediate to the edges 15 and 17 via flexible anchor tie strips 27. Thus, the film 21 is heat sealed to lateral edge 29 of tie strip 27 while the opposite lateral edge 28 of tie strip 27 is heat sealed to the skin 13. The anchor ties 27 typically may comprise a thermoplastic thin material, such as for example, the same polyvinyl chloride film as is used for film 21. As a consequence of this structural arrangement, it is apparent that when the section 11 is in its inflated or expanded condition, the film 21 will be extended in a relatively taut fashion as shown in FIG. 1 between edges 15 and 17 and will establish a surface approximately parallel to the skin 13 and spaced therefrom by a distance approximately equal to the transverse width of the anchor tie strips 27. By such extension of film 21, a relatively thin and uniform air space 25 is established between the skin 13 and film 21 which provides effective insulation that severely inhibits the flow of heat through the air structure walls. It is pointed out at this time that the tie strips 27 are not essential features of this invention since the film 21 could in some instances be directly heat sealed to the skin 13 without too much loss of overall insulating efficiency. The tie strips 27 are useful and desireable however since they (a) inhibit the heat loss and moisture condensation that would otherwise occur in the attachment regions (b) they permit the establishment of uniform air spaces of any desirable thickness and (c) they facilitate the storage and handling of the deflated air structure by permitting the flat folding of the outer skin 13, unrestrained by the smaller dimensions of the film 21. For this reason, tie strips will generally be employed in the preferred embodiments hereinafter described but should not be construed as limiting the scope of the invention.
FIGS. 2 and 2a, similar to FIG. 1, set forth in highly schematic fashion the manner in which the principles of the present invention are applied to a spherical concave section 31 of an inflated structure. The section 31 in this case may be regarded either as a complete air inflated structure or alternatively as a very limited section of the structure in question.
In the present instance, the spherical skin 33 of the inflated structure is secured to the base of the structure along perimeter 41. A thin film 35 is secured to the spherical skin 33 in a manner similar to that discussed in connection with FIG. 1. More specifically, a generally spherically shaped film 35, whose radius of curvature is somewhat less than that of the spherical skin 33, is secured at the base of the structure along the perimeter 42 and separated from the skin by a small distance d. The highest point 38 of the film 35 is secured to the highest point 39 of the skin 33 by a short filamentary anchor tie 40. Additionally, anchor tie strips 43 are employed at the two intermediate locations shown. The plastic film 35 is heat sealed to the anchor tie strips 43 along the edges 34 while the skin 33 is heat sealed to the tie strips along the edges 32. When the skin 33 is in its inflated condition, it will extend the plastic film 35 into a relatively taut surface which will be spaced from the outer skin 33 by a distance determined by the anchor ties. In this manner, air spaces 36 will be created between the film 35 and the skin 33 which will restrict the heat flow from or to the enclosed volume.
In FIG. 3, an isometric view appears of an inflated structure 49 particularly suited for use with the present invention. To the extent shown in FIG. 3, the external aspects of structure 49 are conventional and are merely set forth herein in order to concretely provide an understanding of the present invention. The structure 49 thus includes an inflated shell 51, the outer skin of which typically comprises the relatively tough, impregnated cloth previously referred to. Structure 49 is of the so-called "sculptured" type, which utilizes a plurality of shroud lines 53, which are drawn about the inflated structure and act to relieve stress in the expanded skin. As is known in the art, the structure 49 also includes a number of entrance and exit ports, such as at 55, which are usually of the revolving door type so as to include appropriate seals for aiding in retention of positive air pressure within the structure.
In FIG. 4, a fragmentary, partially sectioned view appears through the wall of the structure of FIG. 3. The view is taken along the line 4-4' of FIG. 3, and illustrates the arrangement of the components utilized in the invention. As seen therein, the relatively thick skin 57 of the inflated structure extends between a pair of shroud lines 59, 61. Because of the positive air pressure within the structure, the skin 57 is seen to be displaced into a billowing arc 62 extending between the said shroud lines. Positioned against the inner side of skin 57 are film-shroud line anchor strips 63 which extend in parallel fashion to the shroud lines, and may be formed of a flexible plastic, as for example polyvinyl chloride. Strip 63 has a thickness of the order of one-half inch and is preferably heat-sealed or otherwise secured to skin 57 at the side adjacent thereto. At the opposite sides of strips 63, a thin plastic film 69, comprising for example a 2 mil polyvinyl chloride or similar thermoplastic material, is heat sealed to strips 63 along the lines such as 65 and 67. The film 69 is continuous along its extension between lines 65 and 67, and in accordance with the principles of the invention previously set forth, is between such boundary lines of lesser extension than is the length of arc 62 defined by skin 57 between shroud lines 59 and 61.
The film 69 is attached to the skin 57 along lines intermediate to the shroud lines 59 and 61, via the anchor tie strips 73 which typically comprise a thin, flexible thermoplastic material similar or identical to that utilized for film 69. The inner lateral edge 77 of the ties 73 is secured to the film 69 as by heat sealing while the outer lateral edge 75 is in like manner secured to the skin 57. In consequence of the structural arrangement described in FIGS. 3 and 4, it will be evident that when skin 57 is fully expanded due to positive air pressure within the structure 49, the thin film 69 will be extended in relatively taut fashion between 65 and 67 thereby sandwiching a thin, uniform and dimensionally stable dead air space 71 between the skin 57 and the thin film 69. It is, of course, this dead air space 71 which in accordance with the invention provides the highly effective insulation which limits the heat flow into and out of the structure 49. In order to provide venting to allow the pressure within the dead air space 71 to equalize to that within the air structure under all circumstances, as during inflation and due to heating effects, a plurality of small venting holes 74 are provided in the film 69.
In FIG. 5, a cross-sectional view appears through an embodiment of the invention similar to that set forth in FIG. 4. The skin 49 shown in FIG. 5 may thus once again represent a portion of an arc extending for example between a pair of shroud lines 59, 61 in FIG. 4. The embodiment shown in FIG. 5 differs from the prior view in that now a plurality of films 81, 83 are secured in parallel spaced fashion to the arc. The films 81, 83 are once again secured to the end line dividing the arc as for example by heat sealing such films to an anchor strip 85.
Anchor ties 87 secure the middle film 81 to the skin 79 by heat sealing along 91 and 89 respectively while anchor ties 86 secure the inner film 83 to anchor ties 87 via heat seals 93 and 91 respectively.
As in prior embodiments, the films 81 and 83 are extended in a relatively taut fashion across the concave surface of billowing, inflated skin 79. The anchor ties 86, 87 merely act as restraints along intermediate points of the film holding such intermediate protions in spaced fashion from the skin to thereby define a plurality of parallelapiped shaped dead air spaces 95 between the films 81, 83 and spaces 96 between the film 81 and skin 79.
FIG. 6 illustrates an embodiment which achieves the objectives of the present invention without the use of distinct anchor tie elements. In this embodiment, the middle film 181 is secured to the anchor strips 185 along lines 182 and is heat sealed to the outer skin 179 along the line 189. The inner film 183 is secured to the anchor strips 185 along lines 184 and is heat sealed to the middle film along lines 193. In much the same manner as previously, as the positive air pressure inflates the air structure, the skin 179 billows outwardly from the restraining shroud lines 159, 161 and extends the middle and inner films in the relatively taut fashion shown. In this case, air spaces of triangular cross section 196 are created between the skin 179 and the middle film 181 while similarly shaped air spaces 195 are created between the middle and inner films.
While the present invention has been particularly set forth in terms of specific embodiments thereof, it will be understood in view of the present disclosure that numerous variations upon the invention are now enabled to those skilled in the art which variations in propriety yet reside within the scope of the present invention.
Thus it will be understood that the term "film" as used herein is not restricted to a homogeneous plastic sheet but may include any relatively impermeable, lightweight sheeting such as for example those formed of foamed plastics the surfaces of which may be sealed if necessary to provide the requisite permeability. Also encompassed within the term "film" are suitably impregnated lightweight fabrics. Accordingly, the invention is to be broadly construed and limited only by the scope and spirit of the claims now appended hereto.
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An air inflated structure, the outer shell walls of which have a surface geometry consisting of one or more concave sections. Heat flow from or into the enclosed volume is drastically curtailed by thin plastic films, which are secured to the outer boundaries of the concave surface sections, and are joined to the shell wall at locations within the boundaries of its curved surface section by direct attachment or via flexible anchor tie strips.
The surface area of each film is less than that of the surface geometry encompassed within the boundary to which it is secured, whereby in its inflated state, the outer shell wall extends the films in a taut fashion across its curved surface geometries to define a thin, uniform and dimensionally stable insulating air space between the shell wall and the plastic films. Additional sets of plastic films, spaced approximately parallel, may be utilized to further curtail the said heat flow.
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RELATED APPLICATIONS
This application claims the benefit of U.S. provisional patent application No. 61/334,639 filed May 5, 2010, which is herein incorporated in its entirety by reference.
TECHNICAL FIELD
The invention relates to slings used with lifters to mobilize a disabled person. More particularly, the invention relates to a rigid sling system whose constituent sections may be slid under the individual and interlocked while the person is in a sitting position, e.g. in a wheelchair, embracing, as opposed to lifting, the individual into a sling and ready to become engaged to any lifting device via adjustable straps.
BACKGROUND
Due to the lack of mobility, a handicapped person is dependent on others. In addition to creating difficulties in completing daily tasks, this dependency also creates hardships for those around them. The lack of mobility and the feeling of burdening others have long term physical and mental effects on both the handicapped person and those around them.
Regardless of the means (e.g. lifter), a type of sling is used to move a disabled person from one point to another. At present, a variety of slings have been designed and are being employed. Existing slings are either too bulky or there is a need to position the disabled person into them, which requires some manual lifting of the subject, or they are made of a type of fabric or strap supports which makes these slings flexible. The flexibility of these slings combined with the compressibility of the disabled person's body requires a long vertical range of movement for the lifting devices to do the actual lifting, resulting in limitations in the usefulness of these types of slings. These slings also exert lateral pressure on the individual's body causing discomfort and possibly affecting circulation in the contact area.
What is needed, therefore, are means to eliminate the disadvantages of the existing slings for lifting a disabled person. The use of a rigid sling system that can be slid comfortably and safely under the disabled person with minimal effort from a lay person and secures the subject without inserting lateral pressure while requiring minimal lifting of the subject is highly desirable. Hence this invention provides a practical solution.
SUMMARY
One embodiment of the invention provides a durable, rigid, lightweight sling system with its constituent sections easily able to slide under a disabled person, then interlock and support the person. All the constituent pieces that come in contact with the person's body are coated with hypoallergenic material. In addition, it is designed to be used for toilet and bathing purposes.
Another embodiment of the invention provides a rigid sling system with a lifting device to use minimal vertical movement to separate the person from the place they are sitting. It also eliminates the lateral forces on the user, thus making the whole process easier and more comfortable.
In another embodiment, the use of such a sling system does not require another individual to lift the disabled person into the sling. Rather, the assistant may place this sling system easily and safely under the subject while the subject is sitting in a wheelchair, car, couch, bed, or office chair. This may be accomplished by simply pushing the disabled person to one side, which will position the buttocks and thigh so the proper section of the sling may be slid under the proper area. This process will be repeated for the opposite side. After both sections are in position and assembled, the sling is ready for use. Note that this assisting person could be almost anyone, man, woman, or young adult.
In another embodiment, when the sling system is used to transfer a disabled person to a car or any other place and one wishes to remove it from under the person, just undo the locking system to detach the left and the right sections of the sling and slide out the constituent sections safely and easily, confident that it can be readily used as needed.
In another embodiment, no tools are required for assembling or disassembling of the sling system. When the sling system sections are detached, it may be transported or stored anywhere without occupying much space.
The features and advantages described herein are not all-inclusive and, in particular, many additional features and advantages will be apparent to one of ordinary skill in view of the drawings, photos, specification, and claims. Moreover, it should be noted that the language used in the specification has been principally selected for instructional purposes, and not to limit the scope of the inventive subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS AND PHOTOS
FIG. 1 is a block diagram illustrating a front view of the two piece sling system, ready to be attached to a lifting device configured in accordance with one embodiment.
FIG. 2A is a block diagram illustrating a front view of a right section of the sling system configured in accordance with one embodiment.
FIG. 2B is a block diagram illustrating a front view of a left section of the sling system configured in accordance with one embodiment.
FIG. 3A is a block diagram illustrating a top view of a grip member 63 of FIG. 3B .
FIG. 3B is a block diagram illustrating a front view of a back side connector configured in accordance with one embodiment.
FIG. 3C is a block diagram illustrating a front view of a grip member of FIG. 4C .
FIG. 3D is a block diagram illustrating a side view of a bracket of FIG. 4C in accordance with one embodiment.
FIG. 4A is a block diagram illustrating a front view of a right leg support member configured in accordance with one embodiment.
FIG. 4B is a block diagram illustrating a front view of a right side main frame configured in accordance with one embodiment.
FIG. 4C is a block diagram illustrating a front view of a front side connector configured in accordance with one embodiment.
FIG. 5A is a block diagram illustrating a front view of FIG. 5C configured in accordance with one embodiment.
FIG. 5B is a block diagram illustrating a top view of FIG. 5C .
FIG. 5C is a block diagram illustrating side view of a back side connector plate of FIG. 3B receiver configured in accordance with one embodiment.
FIG. 6 is a block diagram illustrating a side view of a left side main frame configured in accordance with one embodiment.
FIG. 7 is a block diagram illustrating a side view of a right side main frame configured in accordance with one embodiment.
FIG. 8 is a photograph of one embodiment of the sling system being interlocked and connected to a lifter.
FIG. 9 is a photograph of the sling system which has been swung to a position inside a vehicle configured in accordance with one embodiment.
FIG. 10 is a photograph of the right section FIG. 2A and the left section FIG. 2B of the sling system configured in accordance with one embodiment.
FIG. 11 is a photograph of a back side connector FIG. 3B , connecting a left side main frame of FIG. 2B and a right side main frame of FIG. 4B via a back connector receiver of FIG. 5C configured in accordance with one embodiment.
FIG. 12 is a photograph of a front side connector FIG. 4C configured in accordance with one embodiment.
FIG. 13 is a photograph of a front side connector FIG. 4C connecting a right leg support member of FIG. 4A and a left leg support member of FIG. 2B configured in accordance with one embodiment.
DETAILED DESCRIPTION
One embodiment of the present invention provides a durable, rigid sling system comprised of a right side main frame 82 of FIG. 4B , a left side main frame 42 of FIG. 2B , a back side connector FIG. 3B , a front side connector FIG. 4C , a right leg support FIG. 4A , a left leg support 46 of FIG. 2B , and straps 20 , 22 , 24 , 30 , 34 , 36 , 38 of FIG. 1 , strap 162 of FIG. 7 and their appropriate buckles and hooks. All parts are configured to be assembled or disassembled without tools in accordance with another embodiment of this invention.
A right side main frame 82 of FIG. 4B , a back side connector FIG. 3B , a right leg support FIG. 4A , and a front side connector FIG. 4C can be grouped using two Carriage bolts-Square neck 40 , 44 of FIG. 2A , and their respective Miniature Clamping knobs 40 A, 44 A of FIG. 2A , and a clamping knob 112 to form the right section FIG. 2A of the sling system. All parts are configured to be assembled or disassembled without tools in accordance with one embodiment of this invention.
The left side main frame 42 of FIG. 2B and the left leg support 46 of FIG. 2B may be grouped together using a carriage bolt-square neck 48 of FIG. 2B with proper miniature clamping knob 48 A of FIG. 2A to form the left section FIG. 2B of the sling system. These members may be disassembled upon demand. All members are configured to be assembled or disassembled without tools in accordance with one embodiment of this invention.
When the left section FIG. 2A and the right sections FIG. 2B of the sling system are connected together, it will support the area under the thigh close to the knee, the buttocks and continuing up the back to the area under the shoulder blades and it resembles a legless chair with an opening in the center. This opening at the center serves two purposes: 1) it facilitates the placement of the sling system sections under the disabled person in accordance with one embodiment and 2) the sling system may be used for toilet and bathing purposes in accordance with another embodiment of this invention.
All the constituent pieces that are subject to come into contact with the body of the disabled person have a hypoallergenic coating in accordance with one embodiment of this invention.
Referring to FIG. 7 , the constituent portion of the right main frame 82 are a right-long frame 83 and a right-side support 93 . The right long frame 83 is hemmed at both ends, a back hem 160 and a front hem 166 . The front hem 166 has a special form 168 and will receive the right leg support 100 of FIG. 4A . The back hem will receive the right side of a back side connector plate 74 of FIG. 3B . The left side support 150 , in addition to providing a side support for a disabled person, also prevents folding of left-long frame 43 . In the right-side support 93 is a cutout 92 of FIG. 4B for the purpose of securing the right side hanging strap 34 of FIGS. 1 and 7 and the short segment of the safety strap 162 of FIG. 7 . The right main frame 82 and its constituent portions 83 and 93 may be made of a thin flat alloy metal, a reinforced plastic, fiberglass, or some other resilient material having a thickness of about 1.5 mm and a width of at least 5 cm. A front view of the right main frame 82 is shown in FIG. 4B .
Referring to FIG. 6 , the constituent portions of the left main frame 42 are a left-long frame 43 and a left-side support 150 . The left long frame 42 has a configured front hem 156 to receive a left leg support 46 of FIG. 2B . The back end of the left-long frame 43 is permanently attached to a back connector-receiving member 131 of FIGS. 5A , 5 C. The left side support 150 , in addition to providing a side support for a disabled person, also prevents folding of left-long frame 43 . In the left-side support 150 is a cutout 158 for the purpose of securing the left side hanging strap 30 of FIGS. 1 and 6 and the long segment of the safety strap 38 of FIGS. 1 and 6 . The left main frame 42 and its constituent portions 43 and 150 may be made of a thin flat alloy metal, a reinforced plastic, fiberglass, or some other resilient material having a thickness of about 1.5 mm and a width of at least 5 cm. A front view of the left main frame 42 is shown in FIG. 2B .
FIGS. 5A and 5B are a front and a top view of FIG. 5C respectively. Referring to FIG. 5C , the back connector receiver member 131 is permanently attached to the back end of the left main frame 42 . It has a guiding member 132 and a latching member 140 . The guiding member 132 has guiding elements 142 , 146 and the latching member 140 has a hook end plate 143 , a push plate 145 for the purpose of unlatching, a counter weight 134 , a stopper 136 and a pivoting pin 138 . FIG. 5B shows that the guiding element 146 has a cutout 144 that serves two purposes. First, it acts as a guide for a notch 64 of a grip member 63 of FIG. 3B to properly pass through and latch on the hook end 143 of the latching element 140 . Second, it secures the grip element 52 of FIG. 3A , preventing the back side connector 74 of FIG. 3B from being disconnected from the receiving member 131 of FIG. 5C when it is in use.
The front view of the front side connecter is presented in FIG. 4C . The bracket 124 is made of alloy steel with a 2-3 mm thickness. It is about 10 centimeter long and has a width and a shape corresponding to the width and the shape of the leg supports 100 of FIG. 4A and 46 of FIG. 2B . This bracket 124 has a strap receiving element 113 , three guiding pins 116 , 118 , 134 , a guiding stud 132 , a safety stud 126 , a clamping knob 112 , bar knob 114 , and two walls 87 , 89 of FIG. 3D . The height of the short wall 89 of FIG. 3D is equal to the thickness of the leg supports 100 , 46 of FIGS. 2A , 2 B respectively, and the height of the other wall 87 of FIG. 3D is around 12 mm. The function of this bracket 124 is to connect and align the leg supports 100 , 46 of FIGS. 2A , 2 B respectively. The pin 134 , with a height of around 15 mm, passes through the right side of the bracket 124 and is secured in a way that the top portion of it is used as a guiding element 134 for the right leg support 100 of FIG. 2A , and the bottom portion is used as the pin 91 of FIG. 3D for pivoting front connector-locking system 130 . After placing the right and the left leg supports in their proper place into the bracket 124 to unify them, the locking system 130 should be pivoted counter-clockwise over the leg supports, then the bar knob 114 is hand tightened for safety purposes. The locking system 130 has a handle 86 and two grip elements 88 , 90 of FIG. 3C . The grip element 90 is also used as a pivoting element for the front side-connector locking system.
FIG. 4A shows the front view of a right leg support 100 . It is made of a thick flat alloy, a reinforced plastic, fiberglass, or some other stiff material, which is about 5 mm thick, 5-6 cm wide and about 20 cm long. The right leg support has a smooth bend 108 in the center along the width. This bend corresponds with the shape of the hem 166 of FIG. 7 and the purpose is to provide a comfort zone under the thigh. It also has an upward curve 96 at the outside end to keep the leg from sliding off. The right leg support 100 has two 6 mm holes 98 , 102 , a 10 mm rounded end groove 104 and a 10 mm bore 108 . After sliding the right leg support 100 through the hem 166 of FIG. 7 , either one of the holes 98 or 102 , in correspondence with the holes 60 , 68 of FIG. 3B may be aligned with the hole 110 of FIG. 4B (depending on the size of the disabled person) and will be secured together by using a 6 mm carriage bolt-square neck 44 and its proper miniature clamping knob 44 A of FIG. 2A . The round groove 104 and the bore 108 will accept the pin 134 and the stud 132 of FIG. 4C respectively upon installation.
FIG. 2B shows the front view of a left leg support 46 positioned in its proper place into the hem 154 of FIG. 6 using a 6 mm carriage bolt-square neck 48 and its proper miniature clamping knob 44 A of FIG. 2B . The shape of the left leg support 46 of one such embodiment is a mirror image of the right leg support 100 with the exception of having only one 6 mm hole 47 in correspondence with the guiding elements 66 , 68 of FIG. 3B . The round end groove 45 and the bore 41 will accept the pins 118 , 116 of FIG. 4C respectively, upon installation. The back side connector plate 74 is made of a thick flat alloy, a reinforced plastic, fiberglass, or some other stiff material which is about 5 mm thick, 5-6 cm wide, and an appropriate length.
FIG. 3B presents the front view of the back side connector. It consists of a back side connector plate 74 and a locking system 61 . The back side connector plate has two cutouts 70 and 78 . These cutouts have their respective lead-in notches 72 and 80 at both ends to guide the back strap 24 of FIG. 1 to pass through and seat it into position, or to remove the back strap 24 from the position in accordance with one embodiment of this invention. The plate 74 has two 6 mm holes, 60 and 78 , two guiding elements 66 and 68 , and around its center has a pivoting pin 76 . The constituent elements of the locking system 61 are: a handle 50 , a pivoting arm 62 , and grip elements 52 , 54 of FIG. 3A . FIG. 3A is the top view of grip member 63 of FIG. 3B . Notice that the grip element 52 of FIG. 3A is longer than the other grip element and at its end has a notch 64 of FIG. 3B . The grip member is made of bend resistant alloy steel.
To install the back side connector FIG. 3B on the right main frame 82 of FIG. 4B the back side connector plate 74 is simply slid into the hem 160 of FIG. 7 , the hole 56 of FIG. 4B is aligned with either holes 60 or 78 of FIG. 3B (in correspondence with the usage of holes 98 or 102 of FIG. 4A for installing the right leg support), then a 6 mm carriage bolt-square neck 40 of FIG. 2A is inserted into the holes and they are secured using miniature clamping knob 40 A of FIG. 2A .
Referring to FIG. 1 , a right hanging strap 34 is coupled to the right-side support 93 through the cutout 92 of FIGS. 4B , and 7 and from the other end, after passing through a configured ring 26 , is threaded through a buckle 10 having a hooked end shape 10 . It also shows the left hanging strap 30 is coupled to the left-side support 150 of FIG. 6 through the cutout 158 of FIG. 6 , and from the other end, after passing through a configured ring 26 A, is threaded through a buckle 16 having a hooked end shape 16 A.
FIG. 1 also shows a front hanging strap 15 . The bottom segment 36 of front hanging strap 15 is coupled to the strap receiving element 113 of FIG. 4C and, from the other end, is threaded through a buckle 32 . Two top segments 20 , 22 of front hanging strap 15 are, from one end, secured to the same buckle 32 and, from the other ends, secured to proper configured hooks 14 , 12 respectively. The back support strap 24 , from one end, snaps on the configured ring 26 of the right hanging strap 34 using an eye hook 18 , then through the configured lead-in notches 70 , 80 sit in the cutouts 72 , 78 and, from the other end, snaps on the configured ring 26 A of the right hanging strap 30 using an eye hook 18 A. The long segment of the safety strap 38 is coupled to the lowest end of the left hanging strap 30 and, from the other end, is free. When the sling system is properly positioned under the person and is lifted from the wheelchair, the long segment of the safety belt 38 should be passed from under the person, threaded through the configured buckle 164 of FIG. 7 , then pulled to tighten before removing the wheelchair
All straps are made of stretch resistant flexible material, but that are soft upon touch, such as heavy duty polyester.
For further clarification, if needed, FIGS. 8 through 13 depict the features and the function of the sections, members, and parts described therein.
The foregoing description of the embodiments of the invention has been presented for the purposes of illustration and description. Each and every page of this submission, and all contents thereon, however characterized, identified, or numbered, is considered a substantive part of this application for all purposes, irrespective of form or placement within the application. This specification is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications and variations are possible in light of this disclosure. For example, straps can be logistic, ratchet, or cam strap, etc., the holes of the back connector plate can have other shapes, such as circular, oval, triangular, etc., the locking system may be replaced by a quick release clamp, etc., and the bar knob may be replaced by a double cam clamp, etc. Thus the scope of the embodiments should be determined by the appended claims and their legal equivalents.
Each of the various embodiments described above may be combined with other described embodiments in order to provide multiple features. Furthermore, while the foregoing describes a number of separate embodiments of the apparatus and method of the present invention, what has been described herein is merely illustrative of the application of the principles of the present invention. Accordingly, this description is meant to be taken only by way of example, and not to otherwise limit the scope of this invention.
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A rigid sling system is provided to ease the lifting of a disabled person by sliding its constituent sections under the subject as opposed to lifting the disabled person into the sling. This sling system is comprised of two sections, a right section and a left section. A right side main frame and its appropriate straps, a back connector, a right leg support, and a front connector with its appropriate straps are constituent members of the right section of the sling system. A left main frame and its appropriate straps, a left leg support are constituent members of the left section of the sling system. The two sections interlock via the connectors and configure to become engaged to a person lifting the sling system.
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BACKGROUND OF THE INVENTION
1. Field of the Present Disclosure
This disclosure relates generally to resistance exercising and in particular to the exercising of muscles of the arms including the biceps and triceps muscles.
2. Description of Related Art Including Information Disclosed Under 37 CFR 1.97 and 1.98
Terpening, U.S. Pat. No. 4,323,232, discloses a method of exercising using an elastic band wherein the band is worn around the wrist just below the hand and includes a protrusion mounted on the inside of the band and positioned to apply pressure to the flexor Capri ulnaris muscle near the base of the hand while the hand is involved in an athletic activity. Vonk, U.S. Pat. No. 5,062,625, discloses a hand exerciser having an elastic structure with loops for receiving all five fingers of one hand at the terminal joint. The loops are connected to a common portion by elastic strips with the thumb essentially in a counterpoised position relative to the other fingers. Exercising is conducted by moving the hand between a flat orientation and a cupped orientation. Kasun, U.S. Pat. No. 6,986,728, discloses an elastic device with four loops connected in a side-by-side arrangement where the loops are sized to engaged four fingers of a hand in the manner of a conventional ring on each finger. The elastic loops are relaxed when the fingers are in side-by-side adjacency, and are stretched when the fingers are spread apart as with the palm of the hand on a flat surface.
The related art described above discloses elastic devices including simple bands which are used for the strengthening of the finders, hand, and wrist for general conditioning and for overcoming disease and malfunction. However, the prior art fails to recognize or teach the method of the present invention whereby, the use of an elastic device held in the hands is able to provide benefit in the exercise and strengthening of the arm muscles. The present disclosure distinguishes over the prior art providing heretofore unknown advantages as described in the following summary.
BRIEF SUMMARY OF THE INVENTION
This disclosure teaches certain benefits in construction and use which give rise to the to objectives described below.
It has been discovered that by rotating the hands against a resistive force it is possible to build strength and provide definition and firming in a person's arms. It has also been discovered that by doing such rotations against resistance, with each hand using leverage against the other hand, such exercise can be conducted with a simple elastic band or series of bands of progressive elastic constant. Therefore, it is believed that the present method is an important advance in the field of muscle training and endurance and athletics providing a low cost and highly convenient exercise technique that may be practiced by persons young and old, healthy or infirm and at any location.
In a first portion of the present method the elastic band is held within clenched fists with the fists positioned palm-to-palm. The hands are then mutually rotated about the axes of the lower arms in opposing directions so that the palms of both hands are facing upward and the blades of the hands are in mutual contact achieving leverage against each other in order to stretch the elastic band. The hands are then rotated back to their initial position palm-to-palm. This simple exercise may be repeated a number of times as desired, and as strength improves, an elastic band with greater resistance may be employed as with protocols for progressive resistive exercising. In an extension of the above movement, the hands may be rotated from the initial palms-touching position to a palms down attitude and this movement may be conducted alternately with the palms-up rotation. The combination of palms-up and palms-down rotations provides an exercise routine for the full range of possible rotation of the hands against resistance and therefore workout of the attendant muscle groups. This series of exercises against resistance focuses on the forearms and biceps muscles of the arms.
In a second portion of the present method the elastic band is held within clenched fists with the fists positioned back-to-back. The hands are then mutually rotated about the axis of the lower arm in opposing directions so that the palms of both hands are facing downward and the index fingers and/or the thumbs of the hands are in mutual contact achieving leverage against each other in order to stretch the elastic band. The hands are then rotating back to their initial positions back-to-back. As with the first portion of the present method, described above, this simple exercise may be repeated a number of times as desired, and as strength improves, an elastic band with greater resistance may be employed to increase the strength of the arm muscles. This provides an exercise routine for the full range of possible rotation of the hands and therefore a workout of the attendant muscle groups. This portion of the present method focuses on the forearm and triceps muscles of the arms.
The elastic band used in the above exercises preferably is a continuous loop with a width about equal to the length of the first and second digits of the adult hand, about one inch; and has an unstretched length of about ten inches, so as to extend through the fists of both hands and also between the hands. The band has an elastic constant capable of working the muscles that are involved in the above described routines, and as with all progressive resistance exercise routines, the resistance to stretching of the elastic band will be selected to adequately work the muscles of the exerciser.
A primary objective inherent in the above described apparatus and method of use is to provide advantages not taught by the prior art.
A further objective is to exercise the muscles of the arms and chest by simple rotations of the hands against resistive forces.
Another objective is to provide an exercise band that is easily wrapped around the hands of a person doing the exercises of this invention method and wherein the exercise band provides an operational elastic restraining force of a magnitude sufficient for working arm muscles in a manner recognized by those of skill in the art as providing standard progressive resistance training benefits.
Other features and advantages of the present invention will become apparent from the following more detailed description, taken in conjunction with the accompanying drawings, which illustrate, by way of example, the principles of the presently described apparatus and method of its use.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)
Illustrated in the accompanying drawing(s) is at least one of the best mode embodiments of the present invention In such drawing(s):
FIG. 1 is a perspective view of the presently described method shown with an unstretched elastic band held in two hands with palms facing and fists clenched;
FIG. 2 is a further perspective view of the two hands of FIG. 1 shown with both of the hands rotated from the positions of FIG. 1 to a palms-up attitude thereby stretching the elastic band;
FIG. 3 is a further perspective view of the two hands of FIG. 1 shown with both of the hands rotated from the positions of FIG. 1 to a palms-down attitude thereby stretching the elastic band;
FIG. 4 is a perspective view of the presently described method shown with the unstretched elastic band held in the two hands with backs of the hands facing and in contact and with fists clenched;
FIG. 5 is a further perspective view of the two hands of FIG. 4 shown with both of the hands rotated from the positions of FIG. 4 to a palms-down attitude thereby stretching the elastic band;
FIG. 6 is a perspective view of a preferred embodiment of the elastic band.
DETAILED DESCRIPTION OF THE INVENTION
The above described drawing figures illustrate the described apparatus and its method of use in at least one of its preferred, best mode embodiment, which is further defined in detail in the following description. Those having ordinary skill in the art may be able to make alterations and modifications to what is described herein without departing from its spirit and scope. Therefore, it should be understood that what is illustrated is set forth only for the purposes of example and should not be taken as a limitation on the scope of the present apparatus and its method of use.
The present invention is an exercise method for application to the human arm muscles and when practiced with the arms close to the body, it exercises the chest muscles as well especially the pectorals. It is presented herein as a means for strengthening, firming and defining the related portions of a person's anatomy. Described now in detail is a method of exercising the muscles of both arms and the chest of a person (a user) using a simple resistance device i.e., an elastic band 10 ; please see FIG. 6 which shows a typical band useful in this invention and which has a band width 12 , a band thickness 14 and a band circumferential length 16 . The elastic band 10 may be a continuous loop, or it may be a simple length of elastic material such as a bungee cord. In this description and in the following claims we refer to the resistance device of this invention as an elastic band 10 , and by this is meant and understood that this terminology refers herein to any elastic fixture that may be applied to the method as described herein.
We refer herein in particular to the biceps and to the triceps muscles of the arms. However, the present method involves almost all of the muscles of the hands, lower arms and wrists, and the upper arms and to some degree the chest as well. In a first position, shown in FIG. 1 , the elastic band 10 is gripped within clenched fists but is unstretched and palms and fingers of the clenched fists are in mutual contact. Next, as shown in FIG. 2 , both of the fists are rotated by 90° simultaneously about the longitudinal axes of the lower arms, into palms-up second positions while keeping the blades, or sides of the clenched fists in contact and thereby stretching the elastic band 10 and exercising the forearms, biceps, etc. Further, from the first position, the clenched fists may be rotated simultaneously into palms-down third positions, as shown in FIG. 3 , keeping thumbs, and, depending on how the thumbs are positioned, the index fingers of the clenched fists in contact, and thereby stretching the elastic band 10 and further exercising the forearms and biceps over a full range of rotation of the fists. The preferred exercise, in a first portion of the method of this invention, is therefore to move from position 1 to position 2, and then back to position 1; and then to position 3, and so-on repetitively.
The previous paragraph describes one portion of the present exercise method. In a second portion of the present exercise method, shown in FIGS. 4 and 5 , the hands grip the elastic band 10 within clenched fists of the user with the elastic band 10 unstretched and with the backs of the hands in contact. This is the fourth position of the method of the present invention. A fifth position, shown in FIG. 5 , is achieved by rotation of the hands over 90° to a palms-down attitude with the index fingers in contact, whereby the elastic band 10 is stretched. Each hand provides leverage against the other in positions two, three and five. This is a unique characteristic of the present method. In the first portion of the exercise method shown in FIGS. 1-3 the arms are bent at the elbow, while in the second portion shown in FIGS. 4 and 5 , the arms are held outstretched.
Either the first or the second portion of the present method, as described above may be used without the other portion to the benefit of the exerciser, but the present method produces full benefit when both portions are included in a workout schedule. It has been found that in particular the biceps and related muscle mass benefits preferentially from the first portion of the present method, while the triceps and its related muscle mass benefits preferentially from the second portion of the present method. When used in the combined method of this invention, the benefit to the arms and related anatomical structures is synergistically complete.
The enablements described in detail above are considered novel over the prior art of record and are considered critical to the operation of at least one aspect of the apparatus and its method of use and to the achievement of the above described objectives. The words used in this specification to describe the instant embodiments are to be understood not only in the sense of their commonly defined meanings, but to include by special definition in this specification: structure, material or acts beyond the scope of the commonly defined meanings. Thus if an element can be understood in the context of this specification as including more than one meaning, then its use must be understood as being generic to all possible meanings supported by the specification and by the word or words describing the element.
When the present inventive method is used in progressive resistance training, sets of repetitions are included in a workout routine, as for instance, every other day conducting three sets of between eight and twelve repetitions of each of the first and the second portions of the method described above with an elastic band that provides enough resistance to allow a workup from eight to twelve repetitions without overstraining the wrists, forearms, biceps or triceps. When twelve repetitions is achievable, an elastic band with an elastic constant that permits only about eight repetitions is substituted for the weaker band and when twelve repetitions with the stronger band is achieved, a yet stronger band is used, and so on.
The definitions of the words or drawing elements described herein are meant to include not only the combination of elements which are literally set forth, but all equivalent structure, material or acts for performing substantially the same function in substantially the same way to obtain substantially the same result. In this sense it is therefore contemplated that an equivalent substitution of two or more elements may be made for any one of the elements described and its various embodiments or that a single element may be substituted for two or more elements in a claim.
Changes from the claimed subject matter as viewed by a person with ordinary skill in the art, now known or later devised, are expressly contemplated as being equivalents within the scope intended and its various embodiments. Therefore, obvious substitutions now or later known to one with ordinary skill in the art are defined to be within the scope of the defined elements. This disclosure is thus meant to be understood to include what is specifically illustrated and described above, what is conceptually equivalent, what can be obviously substituted, and also what incorporates the essential ideas.
The scope of this description is to be interpreted only in conjunction with the appended claims and it is made clear, here, that each named inventor believes that the claimed subject matter is what is intended to be patented.
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An exercise routine includes holding an elastic band in clenched fists and rotating the fists against the elastic restraining force of the elastic band while obtaining leverage through the contact of both hands. In one approach the right arm is rotated in the clockwise direction while in another approach the right arm is rotated in the counter-clockwise direction. The left arm rotates in the opposite sense to that of the right arm. By rotating the fists, wrists, and lower arms against elastic force, the biceps and triceps muscles are worked, and by repeating the exercise over a controlled program of repetitions and sets with increasing resistance, the arm muscles can be strengthened.
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BACKGROUND OF THE INVENTION
The present invention relates to a stator coil support device of an electric rotating machinery wherein an elastic member is inserted between a stator coil and a wedge.
In the most recent electric rotating machineries such as turbine generators, it becomes possible to increase capacity (output) thereof, as compared with the prior art, in accordance with the progressing of cooling technology.
However, increasing capacity of turbine generators has brought about an abrupt increase in a current flowing in the stator coil. Consequently, electromagnetic vibrations of double frequency are generated in the slot of the stator core in which the stator core is installed during a normal operation, and in the event of an abnormal operation at a time, for example, when a short circuiting or like occurs, excessive transient electromagnetic force is generated.
In a conventional turbine generator, such abnormal phenomenon has been dealt with by adopting a structure shown in FIGS. 16 to 19 for the stator coil support device.
With reference to FIGS. 16 to 19 , in the stator coil support device, a stator coil 3 is installed in a slot 2 of a stator core 1 constituted by superimposing thin sheets, for example, sheets of silicon steel, along an axial direction thereof and, at one end of the stator coil 3 installed in the slot 2 , as shown by way of example in FIGS. 16 to 18 , the slot 2 has an opening which is closed by a wedge 6 having inclined surfaces, with an elastic plate 4 and a sliding plate 5 formed with an inclined shape being inserted. The elastic plate 4 is called a ripple spring formed as an undulating (wave-shaped) laminated plate formed through a hot press forming process of a thermosetting resin such as phenol or epoxy resin with cotton or glass cloth etc being as base material. The electromagnetic vibrations generated during the operation are arranged to be suppressed by skillfully utilizing the elastic force due to the undulations of the elastic plate 4 .
Further, in a conventional stator coil support device, the electromagnetic vibrations are suppressed in the same way as described above by mounting the elastic plate 4 as shown in FIG. 18 also on the side surface of the stator coil 3 shown in FIG. 16 with an insulating layer, not shown, being inserted.
In this way, in a conventional stator coil support device, the electromagnetic vibrations have been suppressed, and a damage to the insulating layer has been prevented by the elastic force of the undulation (wave-shape) of the elastic plate 4 which is inserted in the gap between the wedge 6 and the stator coil 3 installed in the slot 2 of the stator core 1 and, in addition, the electrical loss or like that accompanies the formation of the gap has been also prevented.
Although the prior art stator coil support device shown in FIGS. 16 to 19 is excellent in the point of well suppressing electromagnetic vibrations generated in the slot of the stator core, the prior art still provided the following problems.
In order to suppress vibrations of the stator coil 3 , the conventional stator coil support device requires the elastic plate 4 , the sliding plate 5 and the wedge 6 , as described above.
However, if the structural components of the stator coil support device become large in number, the time required for assembling the components increases and more time is spent in the assembling operation, which has repercussions on costs, leading to a problem of high cost. In particular, in regard to the structural components employed in the stator coil support device, it is required for a worker to make simple the operation due to the fact that the assembling operation is generally performed in a restricted location.
SUMMARY OF THE INVENTION
An object of the present invention is to substantially eliminate defects or drawbacks encountered in the prior art mentioned above and to provide a stator coil support device for an electric rotating machinery (rotary electric machine) in which simplification of the assembling operation is achieved by reducing the number of structural components.
This and other objects can be achieved according to the present invention by providing, in one aspect, a stator coil support device for an electric rotating machinery, comprising:
a stator core provided with a slot having an opening;
a stator coil installed in the slot of the stator core;
a wedge member disposed so as to close the opening of the slot of the stator core; and
an elastic member inserted between the stator coil and the wedge member,
wherein the wedge member is formed so as to have an inclination towards an axial direction of the stator core and the elastic member has a structure undulating towards the axial direction.
In another aspect, there is provided a stator coil support device for an electric rotating machinery, comprising:
a stator core provided with a slot having an opening;
a stator coil installed in the slot of the stator core;
a wedge member disposed so as to close the opening of the slot of the stator core; and
an elastic member inserted between the stator coil and the wedge member,
wherein the wedge member is formed so as to have an inclination towards an axial direction of the stator core, the elastic member has a recess, in cross-section, at a central portion thereof, and flanges are provided on both sides of the recess in an inclined manner towards the axial direction.
In a further aspect, there is also provided a stator coil support device for an electric rotating machinery, comprising:
a stator core provided with a slot having an opening;
a stator coil installed in the slot of the stator core;
a wedge member disposed so as to close the opening of the slot of the stator core; and
an elastic member inserted between the stator coil and the wedge member,
wherein the wedge member is formed so as to have an inclination towards an axial direction of the stator core and the elastic member is formed as a split cylinder structure having an inclination towards the axial direction of the stator core.
In a still further aspect, there is also provided a stator coil support device for an electric rotating machinery, comprising:
a stator core provided with a slot having an opening;
a stator coil installed in the slot of the stator core;
a wedge member disposed so as to close the opening of the slot of the stator core; and
an elastic member inserted between the stator coil and the wedge member,
wherein the wedge member is formed so as to have an inclination towards an axial direction of the stator core and the wedge member is formed so as to have an inclination towards the axial direction and provided with ratches on the inclined side, and wherein the elastic member has a plate structure having a recess, in a cross-section, at a central portion thereof, flanges are provided on both sides of the recess and ratches are provided on the flanges, which are formed in an inclined manner towards the axial direction.
In a still further aspect, there is provided a stator coil support device for an electric rotating machinery, comprising:
a stator core provided with a slot having an opening;
a stator coil installed in the slot of the stator core;
a wedge member disposed so as to close the opening of the slot of the stator core; and
an elastic member inserted between the stator coil and the wedge member,
wherein the elastic member has a recess, in cross section, into which said wedge member is fitted.
In a still further aspect, there is also provided a stator coil support device for an electric rotating machinery, comprising:
a stator core provided with a slot having an opening;
a stator coil installed in the slot of the stator core;
a wedge member disposed so as to close the opening of the slot of the stator core; and
an elastic member inserted between the stator coil and the wedge member,
wherein the elastic member is provided with a recess, in cross-section, which is formed with a side to be engaged with a groove formed to the wedge member.
In a still further aspect, there is also provided a stator coil support device for an electric rotating machinery, comprising:
a stator core provided with a slot having an opening;
a stator coil installed in the slot of the stator core;
a wedge member disposed so as to close the opening of the slot of the stator core; and
an elastic member inserted between the stator coil and the wedge member,
wherein the stator coil in the slot of the stator core is covered by the elastic plate with said wedge interposed therebetween, the elastic member is provided with a recess, in cross-section, and flanges are provided on both sides of the recess to be engaged with a groove formed to both slot sides of the stator core.
In preferred embodiments of some of the above aspect, the elastic member has a plate structure having at least one wave-peak, and in a certain case, the elastic member has a plurality of wave-peaks which have heights gradually increasing along the axial direction of the stator core.
The wedge member has an inclination towards the axial direction of the stator core in a range of not less than 0° but not more than 10°. The elastic member has a plate structure having an inclination towards the axial direction of stator core in a range of not less than 0° but not more than 10°.
The recess is formed in a trapezoidal shape. The wedge member is formed in a polygonal shape so as to be fitted into the recess formed in the elastic member by utilizing sides of the polygonal shape.
The elastic member has a plate structure made of glass fiber reinforced plastic material. The elastic member has a plate structure made of non-magnetic stainless-steel material.
According to the stator coil support device for the electric rotating machinery according to the present invention of the aspects and characters mentioned above, the stator coil installed in the slot of the stator core can be supported by the wedge with the elastic plate being inserted. Therefore, the number of structural components can be reduced, so that the assembling operation can be facilitated, thus making it possible to shorten the time required for the assembling operation compared with the conventional technology.
The nature and further characteristic features of the present invention will be made more clear from the following descriptions made with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a perspective view illustrating a first embodiment of a stator coil support device for an electric rotating machinery according to the present invention;
FIG. 2 is a schematic longitudinal section taken along the line II—II of FIG. 1;
FIG. 3 is a view illustrating an elastic plate employed in a first embodiment of a stator coil support device for an electric rotating machinery according to the present invention;
FIG. 4 is a front view illustrating a second embodiment of a stator coil support device for an electric rotating machinery according to the present invention;
FIG. 5 is a side view seen in the direction of arrows V—V of FIG. 4;
FIG. 6 is a perspective view illustrating an elastic plate applied to a second embodiment of a stator coil support device for an electric rotating machinery according to the present invention;
FIG. 7 is a view illustrating a modified example of the elastic plate applied to the stator coil support device;
FIG. 8 is a side view seen in the direction of arrows VIII—VIII of FIG. 7;
FIG. 9 is a front view illustrating a third embodiment of a stator coil support device for an electric rotating machinery according to the present invention;
FIG. 10 is a side view seen in the direction of arrows X—X of FIG. 9;
FIG. 11 is a view illustrating the elastic plate applied to the third embodiment of a stator coil support device;
FIG. 12 is a side view seen in the direction of arrows XII—XII of FIG. 11;
FIG. 13 is a front view illustrating a fourth embodiment of a stator coil support device for an electric rotating machinery according to the present invention;
FIG. 14 is a front view illustrating a first modified example of the fourth embodiment of a stator coil support device for an electric rotating machinery;
FIG. 15 is a front view illustrating a second modified example of the fourth embodiment of a stator coil support device;
FIG. 16 is a front view illustrating one example of a conventional stator coil support device for an electric rotating machinery;
FIG. 17 is a side view seen from the direction of arrows XVII—XVII of FIG. 16;
FIG. 18 is a front view illustrating another example of a conventional elastic plate applied to a stator coil support device for an electric rotating machinery; and
FIG. 19 is a perspective view illustrating a further example of a conventional stator coil support device for an electric rotating machinery.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereunder, embodiments of a stator coil support device of an electric rotating machinery according to the present invention will be described by way of preferred examples with reference to the accompanying drawings.
FIG. 1 to FIG. 3 are diagrams illustrating a first embodiment of a stator coil support device for an electric rotating machinery according to the present invention.
With reference to FIGS. 1 to 3 , the stator coil support device for an electric rotating machinery according to this embodiment has a construction in which a stator coil 12 is installed in a slot 11 of a stator core 10 formed by overlaying thin sheets, for example, silicon steel sheets, along the axial direction of the stator core 10 , and an opening of the is closed by a wedge (wedge means) 14 having an inclined surface with the elastic plate 13 being inserted at one end of the stator coil 12 in a manner shown in FIG. 2 .
The elastic plate 13 is formed, through a hot pressing of thermosetting resin such as phenol or epoxy resin, by using, as a base material, cotton or glass cloth as shown in FIG. 3 . The elastic plate 13 has at least one peak (mount portion) so that peaks are formed by using an undulating (wave-shaped) laminated plate so as to be increased in height in the axial direction of the stator core. Further, the elastic plate 13 may be manufactured or made of glass fiber reinforced plastic material or non-magnetic stainless steel material.
As shown in FIG. 2, the wedge 14 is manufactured through a molding process with an angle of inclination such that its thickness decreases in the axial direction of the stator core. This angle of inclination is not less than 0° and not more than 10°. This numerical range is a preferred applicable range which was determined through experiment.
In this embodiment, the stator coil 12 is supported by the wedge 14 which is molded and processed with an angle of inclination so as to decrease its thickness in the axial direction thereof, and the undulating (wave-shaped) laminated elastic plate 13 having at least one or more peaks, which become higher in the axial direction, is inserted. Accordingly, even if electromagnetic vibration is generated in the stator coil 12 , the elastic force of the elastic plate 13 having at least one or more peaks and the frictional force that accompanies the increase in contact area of the wedge 14 formed with such angle of inclination as mentioned above can be effectively utilized, thereby enabling the vibration to be suppressed.
Furthermore, in this embodiment, the elastic plate 13 among the elastic plate 13 and the wedge 14 which support the stator coil 12 is molded and processed with at least one or more peaks so as to become higher in the axial direction, and, on the other hand, the wedge 14 is molded and processed so as to become thinner in the axial direction. Accordingly, the number of structural components can be reduced, and, as well as control of vibration, the assembling operation can be facilitated, thereby enabling the time required for the assembling operation to be shortened compared with the conventional technology.
FIG. 4 to FIG. 6 are views representing a second embodiment of a stator coil support device for an electric rotating machinery according to the present invention, in which like reference numerals are added to portions or components corresponding to those of the first embodiment and the details thereof are omitted herein.
In the stator coil support device for an electric rotating machinery according to this second embodiment, the stator coil 12 that is installed in the slot 11 of the stator core 10 is supported by the elastic plate 13 and the wedge 14 , as well shown in FIG. 6 . The elastic plate 13 is formed with at least one or more recesses 15 at a central portion having a trapezoidal shape in its cross sectional area, and flat flanges 16 a , 16 b are provided on both sides thereof. As shown in FIG. 5, the elastic plate 13 is molded and processed with an inclined side 17 having an angle of inclination of not less than 0° and not more than 10° with respect to the axial plane.
Furthermore, as shown in FIG. 5, the wedge 14 is molded and processed with an angle of inclination of not less than 0° and not more than 10° towards the axial direction so as to accord with the inclined side 17 of the elastic plate 13 .
Thus, in this embodiment, the elastic plate 13 is molded and processed so as to be provided with at least one or more trapezoidal recesses 15 at the central portion thereof, and the flat flanges 16 a , 16 b are formed on both sides thereof with an inclined side 17 having an angle of inclination of not less than 0° and not more than 10° with respect to the axial plane. On the other hand, the wedge 14 has an angle of inclination of not less than 0° and not more than 10° in the axial direction so as to accord with the shape of elastic plate 13 . Accordingly, the number of structural components can be reduced, and moreover, in accordance with the increase in compressive force with respect to external force from outside at a time of molding the recess 15 of the elastic plate 13 , the assembling operation can be facilitated and the time required for the assembling operation can be shortened compared with the conventional technology.
Although, in the described embodiment, the trapezoidal recess 15 is formed at the central portion of the cross-section of the elastic plate 13 and the flat flanges 16 a and 16 b are provided on both sides thereof, there is no restriction to this example, and for example, as shown in FIG. 7, it could be molded and processed into a split-type cylinder 18 with an inclined surface having an angle of inclination in the range of 0° to 10° in the axial direction as shown in FIG. 8 .
FIG. 9 to FIG. 12 are views representing a third embodiment of a stator coil support device for an electric rotating machinery according to the present invention, in which like reference numerals are added to portions or components corresponding to those of the first embodiment and the details thereof are omitted herein.
In a stator coil support device for an electric rotating machinery according to this third embodiment, at a time of supporting the stator coil 12 installed in the slot 11 of the stator core 10 by interposing the elastic plate 13 and the wedge 14 which are shown in FIG. 11, the elastic plate 13 is formed with at least one or more trapezoidal recesses 15 at the central portion of its cross-section, and flat flanges 16 a , 16 b are provided on both sides thereof. As shown in FIG. 12 , the elastic plate 13 is molded with an inclined side 17 having an angle of inclination of not less than 0° and not more than 10° with respect to the axial plane, and furthermore, is formed with a ratchet-like ratches 19 a to the flanges 16 a , 16 b.
As shown in FIG. 10, the wedge 14 is molded so as to provide an angle of inclination of not less than 0° and not more than 10° in the axial direction so as to accord with the inclined side 17 of the elastic plate 13 and is formed with the ratchet-like ratches 19 b so as to accord with the flanges 16 a , 16 b of the elastic plate 13 .
According to the manner mentioned above, in the present embodiment, the elastic plate 13 in the elastic plate 13 and the wedge 14 which support the stator coil 12 is provided with at least one or more trapezoidal recesses 15 in cross-section and the ratches 19 a are provided in the flat flanges 16 a , 16 b on both sides thereof. On the other hand, the wedge 14 has an angle of inclination of not less than 0° and not more than 10° in the direction of the axial plane so as to accord with the shape of the elastic plate 13 and is equipped with the ratches 19 a . Accordingly, the number of structural components can be reduced and, as a result, the assembling operation can be facilitated while preventing the separation of the elastic plate 13 from the wedge 14 through the engagement of the ratches 19 a of the elastic plate 13 with the ratches 19 b of the wedge 14 . Thus, the time required for the assembling operation can be shortened compared with the conventional technology.
FIG. 13 is a diagram illustrating a fourth embodiment of a stator coil support device for an electric rotating machinery according to the present invention, in which like reference numerals are added to portions or components corresponding to those of the first embodiment and the details thereof are omitted herein.
In the stator coil support device for an electric rotating machinery according to this fourth embodiment, the stator coil 12 installed in the slot 11 of the stator core 10 is supported by the elastic plate 13 and the wedge 14 , and the elastic plate 13 is formed with trapezoidal recesses 15 in its cross-sectional plane. The wedge 14 is fitted by utilizing the polygonal shapes having a large number of sides such as, for example, hexagonal shapes on sides 20 a and 20 b of the recess 15 .
Thus, in this fourth embodiment, the elastic plate 13 in the elastic plate 13 and the wedge 14 which support the stator coil 12 has the cross-section formed as a trapezoidal recess 15 , and the wedge 14 is fitted by utilizing the side of the polygonal shape of the recess 15 , thus reducing the number of structural components. Consequently, the assembling operation can be facilitated and the time required for the assembling operation can be shortened compared with the conventional technology.
Although, in this embodiment, the polygonal wedge 14 having a large number of sides is fitted to the elastic plate 13 provided with the trapezoidal recess 15 , the present invention is not limited to such example, and for instance, as shown in FIG. 14, it would be possible to mold the elastic plate 13 having the recess 15 to be comparatively small in size and to engage the sides 20 a , 20 b of the elastic plate 13 with the grooves 21 a , 21 b formed in the polygonal wedge 14 . Alternatively, for example, as shown in FIG. 15, the wedge 14 can be inserted to the stator coil 12 and supported by being subjected to pressure on the stator coil 12 from the elastic plate 13 formed with the trapezoidal recess 15 at the central portion of its cross-section, with the flanges 16 a , 16 b being provided on both sides thereof so as to be engaged with the grooves 22 a , 22 b of the stator core 10 .
All the examples are beneficial in that the number of structural components is reduced and, hence, facilitates the assembling operation, and the spatial distance in the vertical direction of the stator coil 12 and the slot 11 is reduced, thereby enabling the conductor installing area ratio of the stator coil 12 to be increased.
Further, it is to be noted that the present invention is not limited to the described embodiments and many other changes and modifications may be made without departing from the scopes of the appended claims.
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An electric rotating machinery is provided with a stator coil support device, which comprises a stator core provided with a slot having an opening, a stator coil installed in the slot of the stator core, a wedge member disposed so as to close the opening of the slot of the stator core, and an elastic plate member inserted between the stator coil and the wedge member. The wedge member is formed so as to have an inclination towards an axial direction of the stator core and the elastic plate member has a structure undulating towards the axial direction.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates in general to the field of information handling systems and, more particularly, to a method and apparatus for ensuring the security and integrity of software and data on an information handling system.
[0003] 2. Description of the Related Art
[0004] As the value and use of information continues to increase, individuals and businesses seek additional ways to process and store information. One option available to users is information handling systems. 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 also vary regarding what information is handled, how the information is handled, how much information is processed, stored, or communicated, and how quickly and efficiently the information may be 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 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.
[0005] In recent years, there has been an increase in the number of information handling systems that are manufactured based on a “build to order” process that allows a customer to specify hardware and software options. Currently, a “build to order” manufacturer often ships information handling systems from the factory to the customer. In the case of smaller customers, the customer may receive the system directly. For larger customers, however, the information handling system may pass through a number of intermediate entities such as value added resellers (VARs).
[0006] In general, there is no assurance for the customer that the contents of the information handling system have not been modified after leaving the originating manufacturing facility. Ensuring the security and integrity of the system contents is essential, however, since the system contents may include confidential customer set-up information including provisioning data, configuration data, and other sensitive information.
[0007] Efforts are underway in the industry to promote secure computing systems. However, there is no current system or procedure for ensuring the initial security of newly manufactured information handling systems from a manufacturing facility to the customer. In view of the foregoing, there is a need for a method and apparatus to ensure the security and integrity of software and data contained on a “build to order” information handling system.
SUMMARY OF THE INVENTION
[0008] The present invention overcomes the shortcomings of the prior art by providing a method and apparatus for ensuring the security of a particular configuration of hardware and software for an information handling system that is assembled using a “build-to-order” system. Specifically, the present invention ensures the security and integrity of data on an information handling system from the point of manufacture to the final destination at the customer's facility.
[0009] The method and apparatus of the present invention is implemented using a plurality of digital keys to generate digital seals and to verify the contents of a predetermined set of data and system parameters contained in a manifest file that is stored in the information handling system. In one embodiment of the invention, the digital seal is generated using asymmetric encryption keys. In an alternate embodiment of the invention, the digital seal is generated using symmetric keys.
[0010] In the embodiment of the invention that is implemented using asymmetric keys, a customer provides their public key at the time an order is placed for an information handling system. The information handling system is then manufactured with the operating system and a predetermined set of software files is installed thereon. When the process of fabricating the information handling system is complete, a manifest file is constructed comprising a plurality of specified files, registry settings, provisioning information, and any additional information needed for a specific level of security. Once the manifest file is complete, it is encrypted with the customer's public key. A one-way hash function is performed on the encrypted manifest file to generate a “digest.” The manufacturer then digitally encrypts this “digest” with a private key that they typically control and keep secret, to create a digital “signature.”
[0011] When the customer's information handling system performs its initial boot, a public key provided by the manufacturer is extracted from secured storage within the information handling system and is then used to verify the manufacturer's digital signature, thereby validating the manifest file. Using the same hashing algorithm that generated the digest sent by the manufacturer, a new signature is generated from the same manifest file. The two signatures are then compared, and if they match, then the manifest file has not been altered since it was signed. If the manifest file has been altered, the initial boot is designated as “tampered/tainted” and the user is notified of the potential for a breach of security. If the system passes the test conducted during the initial boot sequence, the system then requests the customer to provide their private key information, which is used to decrypt the information contained in the manifest file.
[0012] In an alternate embodiment of the invention, the digital seal is generated using a symmetric key. In this embodiment, the information handling system is manufactured with the operating system and a predetermined set of software is installed thereon. When the process of fabricating the information handling system is complete, a manifest file is constructed comprising a plurality of specified files, registry settings, provisioning information, and any additional information needed for a specific level of security. The manufacturer first encrypts the manifest file with a symmetric key. The resulting encrypted manifest file is then digitally “signed” with the same symmetric key, which is provided to the customer at the time of purchase. When the information handling system performs its initial boot, the customer is prompted to enter the symmetric key provided by the manufacturer, which is then used to decrypt the manufacturer's manifest. Additionally, using the same hashing algorithm that generated the digest sent by the manufacturer, a new digest is generated from the same manifest file. The two digests are then compared, and if they match, then the manifest file has not been altered since it was signed. If any of the information compared to the manifest has been altered, the initial boot is designated “tampered/tainted” and the user is notified of the potential for a breach of security. If the system passes the test conducted during the initial boot sequence, the system then prompts the customer to authorize decryption of the manifest file using the same symmetric key.
[0013] The alternate embodiment comprising a symmetric key has the advantage of maximizing flexibility. For example, the symmetric key embodiment can be used for a dealer or a vendor who can print out the key for a customer. As discussed herein, the symmetric key in combination with information stored in the computer provides a comprehensively secure system since the end user must have physical possession of the computer in order to initiate the initial boot sequence using the symmetric key.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The present invention may be better understood, and its numerous objects, features and advantages made apparent to those skilled in the art by referencing the accompanying drawings. The use of the same reference number throughout the several figures designates a like or similar element.
[0015] FIG. 1 is a general illustration of an automated build-to-order system for installing software on an information handling system.
[0016] FIG. 2 is a system block diagram of an information handling system.
[0017] FIG. 3 is an illustration of the key components of a secure data delivery system for an information handling system using a Trusted Platform Module (TPM).
[0018] FIG. 4 is an illustration of alternate delivery pathways for information handling systems implementing the data security system of the present invention.
[0019] FIG. 5 is a flowchart illustration of the steps implemented in the method and apparatus of the present invention.
DETAILED DESCRIPTION
[0020] FIG. 1 is a schematic diagram of a software installation system 100 at an information handling system manufacturing site. In operation, an order 110 is placed to purchase a target information handling system 120 . The target information handling system 120 to be manufactured contains a plurality of hardware and software components. For instance, target information handling system 120 might include a certain brand of hard drive, a particular type of monitor, a certain brand of processor and software. The software may include a particular version of an operating system along with all appropriate driver software and other application software along with appropriate software bug fixes. Before target information handling system 120 is shipped to the customer, the plurality of components are installed and tested. Such software installation and testing advantageously ensures a reliable, working information handling system which is ready to operate when received by a customer.
[0021] Because different families of information handling systems and different individual computer components require different software installation, it is necessary to determine which software to install on a target information handling system 120 . A descriptor file 130 is provided by converting an order 110 , which corresponds to a desired information handling system having desired components, into a computer readable format via conversion module 132 .
[0022] Component descriptors are computer readable descriptions of the components of target information handling system 120 which components are defined by the order 110 . In an embodiment of the present invention, the component descriptors are included in a descriptor file called a system descriptor record which is a computer readable file containing a listing of the components, both hardware and software, to be installed onto target information handling system 120 . Having read the plurality of component descriptors, database server 140 provides a plurality of software components corresponding to the component descriptors to file server 142 over network connection 144 . Network connections 144 may be any network connection well-known in the art, such as a local area network, an intranet, or the internet. The information contained in database server 140 is often updated such that the database contains a new factory build environment. The software is then installed on the target information handling system 120 . The software installation is controlled by a software installation management server that is operable to control the installation of the operating system and other software packages specified by a customer.
[0023] FIG. 2 is a generalized illustration of an information handling system, such as the target information handling system 120 illustrated in FIG. 1 . The information handling system includes a processor 202 , input/output (I/O) devices 204 , such as a display, a keyboard, a mouse, and associated controllers, a hard disk drive 206 , other storage devices 208 , such as a floppy disk and drive and other memory devices, and various other subsystems 210 , and a trusted platform module (TPM), such as a microcontroller used to store keys, passwords, digital certificates, and other security mechanisms, all interconnected via one or more buses 212 . The software that is installed according to the versioning methodology is installed onto hard disk drive 206 . Alternately, the software may be installed onto any appropriate non-volatile memory. The non-volatile memory may also store the information relating to which factory build environment was used to install the software. Accessing this information enables a user to have additional systems corresponding to a particular factory build environment to be built.
[0024] For purposes of this disclosure, an information handling system may include any instrumentality or aggregate of instrumentalities operable to compute, classify, process, transmit, receive, retrieve, originate, switch, store, display, manifest, detect, record, reproduce, handle, or utilize any form of information, intelligence, or data for business, scientific, control, or other purposes. For example, an information handling system may be a personal computer, a network storage device, or any other suitable device and may vary in size, shape, performance, functionality, and price. The information handling system may include random access memory (RAM), one or more processing resources such as a central processing unit (CPU) or hardware or software control logic, ROM, and/or other types of nonvolatile memory. Additional components of the information handling system may include one or more disk drives, one or more network ports for communicating with external devices, as well as various input and output (I/O) devices, such as a keyboard, a mouse, and a video display. The information handling system may also include one or more buses operable to transmit communications between the various hardware components.
[0025] FIG. 3 is an illustration of the key components of a secure data delivery system for an information handling system. The hard drive 206 comprises a partition wherein information relating to the configuration of the information handling system is stored. A manifest file 216 comprises a plurality of files relating to the information handling system. For example, the manifest file 216 can include information relating to a processor serial number 217 , information relating to the system BIOS 218 and other configuration information stored in CMOS 220 . In addition, a predetermined selection of files 222 , including configuration registers and other customer defined data is stored on the manifest 216 . A digital signature file, sometimes referred to herein as a digital “seal,” 224 is also stored on the hard drive 206 . The digital seal provides an authentication of the contents of the manifest file and any tampering with the contents of the manifest file will result in the digital seal being “broken.” In addition, a kernel for the operating system used in the first boot 226 is stored on the hard drive 206 and information relating to the digital key 228 may be stored on Trusted Platform Module (TPM) 214 , which is typically a microcontroller capable of storing digital keys, passwords, digital certificates and other security mechanisms. In some embodiments of the invention, encryption keys will be stored on the hard drive 206 , but will be further encrypted, or “sealed,” using security mechanisms either stored in, or comprising, TMP 214 . In some embodiments of the invention, the digital key 228 will comprise the public key of a manufacturer in accordance with public key protocols.
[0026] In one embodiment of the present invention, the security is based on a public key system. In an alternate embodiment however, a customer can order a system from the manufacturer over a secure SSL-protected link. If the customer does not have a public key, the customer can request a symmetric key instead, which is displayed on a web page and can be saved or printed by the customer. Using a secure socket layer (SSL) security system, information relating to the symmetric key is maintained in a secure environment.
[0027] When the information handling system 120 arrives at the customer's site, the customer uses the symmetric key, which must match the same symmetric key as is stored by the manufacturer on the TPM 214 to “break the seal.” The symmetric key embodiment is particularly useful for consumers who may not have a public key or do not know how to use one. For example, if the computer is a gift, the customer can print out the key and give it to the recipient of the gift. Even if the key is exposed through unsecured e-mail, it is necessary to have physical possession of the computer to use it, as the matching key is securely stored in TPM 214 . This embodiment also avoids the positive verification requirement of obtaining a copy of the manufacturer's public key directly from the Internet or relying on the key being stored unencrypted on the hard drive. The alternate embodiment comprising a symmetric key also has the advantage of maximizing flexibility. For example, the symmetric key embodiment can be used for a dealer or a vendor who can print out the key for a customer. As discussed hereinabove, the symmetric key in combination with information stored in the computer provides a comprehensively secure system since the end user must have physical possession of the computer in order to initiate the initial boot sequence using the symmetric key.
[0028] The contents of the manifest file 216 and the level of security verification can vary depending on predetermined security parameters selected by the manufacturer or the customer for a desired level of security. For example, at one level of security, the security information can comprise signed configuration files and a manifest file containing a predetermined set of operating system and boot files. At this level of security, the initial boot security can include a checksum verification of the BIOS and the CMOS, and the verification can be conducted with or without the public key of the end user. In another level of security, the security information can include a signed checksum of the entire hard drive 206 , and a checksum verification of the entire hard drive and the BIOS and CMOS during the initial boot. This level of security can also be implemented with or without the public key of the end user. A third level of security can include encrypted customer configuration files, signed operating system and boot files, and various checksum verifications performed using digital keys in accordance with public key protocols. A fourth level of security can include encrypted customer configuration files, a signed checksum of the entire hard drive 206 , and a checksum verification of the BIOS and CMOS using digital keys in accordance with public key protocols.
[0029] FIG. 4 is an illustration of alternate delivery pathways for information handling systems implementing the data security system of the present invention. In one embodiment of the invention, an information handling system can be delivered directly from a manufacturing facility 400 to a customer 402 . The information handling system 120 includes a manifest file 216 , the manufacturer's digital seal 224 , and one or more encryption keys stored on TPM 214 . In an alternate embodiment of the invention, the information handling system 120 is delivered to an intermediate destination 404 , which can be a consultant or a value added reseller (VAR) that modifies the information handling system 120 by installing a specialized set of software and/or hardware enhancements. After the enhancements have been added to the information handling system, the VAR will install a modified manifest file 216 , a modified digital seal 224 , and one or more additional encryption keys on TPM 214 , all on the information handling system 120 a as described hereinabove. The information handling system 120 a can then be delivered to the customer 402 or can be delivered to another intermediate destination 403 n for additional hardware and software modifications. After the enhancements have been added to the information handling system, each of the intermediate VARs will install a modified manifest file 216 , a modified digital seal 224 , and one or more additional encryption keys on TPM 214 , all on the information handling system 120 a in accordance with the present invention. Once the information handling system 120 a arrives at the customer 402 , an initial boot sequence is initiated and the integrity of the data on the information is verified as described hereinabove. The final version of the modified digital seal 224 contains information that can be used to establish a “chain of title” to document the modifications made to the information handling system 120 a by each of the intermediate VARs. Moreover, the present invention can be used to “roll back” signatures to identify individual digital signatures for each entity that modified the information handling system 120 a in its path from the manufacturer 400 to the final user 402 through the use of the original and subsequent encryption keys stored on TPM 214 .
[0030] FIG. 5 is a flowchart illustration of the steps implemented in the method and apparatus of the present invention. In step 502 , the system is posted and a minimal operating system is loaded in step 506 . In step 508 , the data security verification program is implemented. In step 510 , the manufacturer-provided public key is obtained from Trusted Platform Module (TPM) 214 , and an algorithm is run in step 512 to authenticate the contents of the manifest file. In step 514 , a test is run to determine whether the various system components match the data contained in the authenticated manifest. If the test conducted in step 514 indicates that the system contents do not match the manifest, a notice of a potential security breach is provided to the user in step 515 . If, however, the test run in step 514 indicates that the system components do match the manifest file, processing continues to step 516 wherein a checksum algorithm is run to verify the contents of the BIOS. In step 518 , a test is conducted to determine whether the results of the checksum operation for the BIOS match the contents of the manifest file. If the test conducted in step 518 indicates that the BIOS does not match the contents of the manifest file, a notice is provided to the user. If, however, the test conducted in step 518 indicates that the BIOS does match the contents of the manifest file, processing continues to step 520 wherein a checksum algorithm is executed to determine whether the contents of the CMOS memory match the contents of the manifest file. In step 522 , a test is conducted to determine whether the checksum algorithm executed in step 520 indicates that the contents of the CMOS memory match the manifest file. If the test conducted in step 522 indicates that the contents of the CMOS memory do not match the manifest file, the user is notified. If, however, the results of the test conducted in step 522 indicate that the contents of the CMOS memory do match the manifest file, processing continues to step 524 wherein a checksum algorithm is executed to use the Public Key—Digital-Break-The-Seal (PK-DBTS) data to confirm whether the digital key matches the manifest file. In step 526 , a test is conducted to determine whether the checksum algorithm executed in step 524 indicates that that PK-DBTS data matches the manifest. If the test conducted in step 526 indicates that the contents of the PK-DBTS data do not match the manifest, the user is notified. If, however, the results of the test conducted in step 526 indicate that the PK-DBTS data does match the manifest, processing continues to step 528 wherein the manufacturer “Digital-Break-The-Seal” algorithm is executed and the user is requested to provide appropriate input to initiate operation of the data handling system. In step 530 , the initial boot of the operating system is conducted and the software for the system is installed on the information handling system. While maximum security is obtained by implementing all of the steps discussed hereinabove, it will be understood by those of skill in the art that a subset of these security and verification steps can be implemented to provide effective security for a particular configuration of hardware and software for an information handling system within the scope of the present invention.
Other Embodiments
[0031] Other embodiments are within the following claims.
[0032] Although the present invention has been described in detail, it should be understood that various changes, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended claims.
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A method and apparatus for ensuring the security of a particular configuration of hardware and software for an information handling system that is assembled using a “build-to-order” system. The present invention ensures the security and integrity of data on an information handling system from the point of manufacture to the final destination at the customer's facility. The information handling system is then manufactured with the operating system and a predetermined set of software being installed thereon. A manifest file is constructed comprising a predetermined set of data files and configuration information. The manifest file is digitally signed with at least one digital key. When the information handling system performs its initial boot, a second digital key, securely stored in a Trusted Platform Module (TPM), is used to extract information from the manifest file and the existing data files and configuration information is compared to the information contained in the manifest file. If any of the information compared to the manifest has been altered, the initial boot is designated as “invalid” and the user is notified of the potential for a breach of security.
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TECHNICAL FIELD
[0001] The present invention relates to a method for the racemization of α-amino acids, in particular a method for the racemization of α-amino acids comprising contacting an organic phase containing a racemization catalyst with an aqueous basic solution containing an optically active α-amino acid in the presence of a phase transfer catalyst.
BACKGROUND ART
[0002] In the production of optically active D- or L-α-amino acids used as a raw material or intermediate, etc. in the field of pharmaceuticals, agriculture and fine chemistry, the amino acid having optical activity may be directly prepared as an optically active isomer with the desired optical activity or, it may be prepared as an optically active isomer having the desired optical activity by preparing a racemic mixture and then subjecting it to an optical resolution method.
[0003] In the process of producing D- or L-α-amino acids by an optical resolution of racemic amino acids, the remaining optical isomers after the optical resolution may usually be subjected to racemization process and then reused as racemic mixtures for an optical resolution for economic reasons.
[0004] Recently, L-amino acid or D-amino acid can be mass-produced by chemical methods or biological methods. In case where such mass-produced L-amino acid or D-amino acid is inexpensive but the L-amino acid or D-amino acid having an opposite steric structure is expensive, the racemization of amino acids may be an important key technology whereby an amino acid having an inexpensive steric structure is transformed to an amino acid having an expensive steric structure.
[0005] As a racemization method of α-amino acid having optical activity, several methods including chemical and biological methods have been disclosed.
[0006] U.S. Pat. Nos. 2,586,154 and 4,769,486 disclose a chemical racemization method wherein α-amino acid is introduced in a strong acid or alkaline aqueous solution and subjected to a racemization at a high temperature. In the methods of these documents, the severe reaction conditions (high temperature, long reaction period) may cause decomposition of α-amino acid and thus many side products are generated. [See Advances in Protein Chemistry, Vol. 4, p. 4339 (1948)].
[0007] As an improved version of the above-described chemical method, U.S. Pat. No. 3,213,106 (1965) has proposed a racemization method wherein α-amino acid is introduced in a closed vessel and subjected to a racemization at a high temperature (100˜150° C.). The method has problems that the reaction temperature is very high above the boiling point of water and thus the reactor needs to be a closed vessel that can endure the high pressure.
[0008] As a further improved method of the above-described chemical method, U.S. Pat. No. 4,401,820 (1983) discloses a racemization method wherein the racemization is more easily carried out at a temperature of 100° C. or less by using organic acids such as formic acid, acetic acid, propionic acid instead of water as a solvent and employing a variety of aldehydes as a catalyst. However, there are problems that the organic acid used as a solvent has a bitter smell and toxicity and thus requires a complicated process for its use and recovery.
[0009] Japanese Patent Laid-Open Publications H11-228512 and H11-322684 (corresponding to European Patent Publication EP 0937705A) disclose a catalytic racemization method wherein a racemization of α-amino acid is carried out by using salicylaldehyde as a catalyst under an acidic condition. In the method of these documents, the yield of α-amino acid is low due to severe reaction conditions.
[0010] Meanwhile, it has been known that a Schiff base obtained by reacting salicylaldehyde or substituted salicylaldehyde with α-amino acid is combined with a copper ion (Cu2+) to give a copper metal complex (Cu-Metal Complex), which can be utilized as a very useful racemization catalyst (Scheme 1). [Bulletin of the Chemical Society of Japan, Vol 51 (8), 2366 (1978); Biochemistry, Vol 17 (16) 3183 (1978); Inorganic Chemistry, Vol 9 (9), 2104 (1970); Bulletin of the Chemical Society of Japan, Vol 42 (9), 2628 (1969); Australian Journal of Chemistry, Vol 19, 2143 (1966)].
[0000]
[0011] The above Cu-metal complex is easy to prepare and is useful as a racemization catalyst since a variety of amino acids can be racemized at the normal temperature even with a small amount under a basic condition in a water solvent. However, the above Cu-metal complex has problems that, when the resultant reaction mixture is acidified in order to isolate racemic α-amino acid, the Cu-metal complex catalyst may be decomposed and thus cannot be recycled and that the salicylaldehyde and copper ion which result from decomposition should be removed during the separation and purification step of α-amino acid.
DETAILED DESCRIPTION OF THE INVENTION
Technical Problem
[0012] The present inventors have studied the existing racemization method of α-amino acids employing copper metal complex as a racemization catalyst and tried to develop an improved way for carrying out the existing racemization method more easily and economically and for reusing the catalyst of copper metal complex without decomposition.
Technical Solution
[0013] The present inventors have found that, when contacting an organic phase containing a copper metal complex as a racemization catalyst with an aqueous phase containing α-amino acid or stirring a two-phase mixture containing them in the presence of a phase transfer catalyst, first, the racemization of α-amino acid can be performed under relatively mild conditions, second, the organic phase and the aqueous phase can be easily separated after the completion of the racemization reaction, third, the organic phase containing the catalyst of copper metal complex can be reused without a decrease of the catalytic activity, forth, the racemized α-amino acid can be easily isolated and purified since the aqueous phase containing racemized α-amino acid does not contains other reactant, and thus, that it is possible to carry out the racemization of α-amino acid in a large scale and at a low cost. As a result, the present inventors have completed the present invention.
Effects of the Invention
[0014] The racemization method of α-amino acid according to the present invention has a high yield due to the mild reaction conditions which result in less decomposition of α-amino acid; allows to recycle the racemization catalyst; enables easy separation and purification of the racemized α-amino acid; and has an economic advantage due to its mass production capability.
Best Mode for Carrying Out the Invention
[0015] The object of the present invention is to provide a method for racemization of α-amino acid which comprises contacting an organic phase containing copper metal complex composed of salicylaldehyde, α-amino acid and copper ion as a racemization catalyst with an aqueous basic phase containing an optically active α-amino acid in the presence of a phase transfer catalyst.
[0016] According to the present invention, said copper metal complex can be represented by the following Chemical Formula 1.
[0000]
[0000] wherein, X represents a hydrogen, a halogen atom such as chloro or bromo, an alkyl group having from 1 to 4 carbon atoms, an alkoxy group having from 1 to 4 carbon atoms or a nitro group, preferably 5-nitro group.
[0017] The copper-metal complex (Cu-Metal Complex) of Formula 1 which can be used as a racemization catalyst can be prepared by known methods. For example, the copper metal complex of Formula 1 can be prepared by reacting alicylaldehyde or its derivatives with amino acid to form a Schiff base and having copper ion coordinated thereto.
[0018] The salicylaldehyde derivative may have one or more diverse substituents on its phenyl ring. By way of examples of the substituents, mention can be made to a halogen atom such as F, Cl or Br, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl, and an alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy or butoxy and a nitro group (NO2). Preferably mention can be made of 5-nitrosalicylaldehyde.
[0019] α-Amino acids to which the racemization of the present invention can be applied can encompass both of natural and non-natural amino acids, unless otherwise specified. As examples of the α-amino acid to which the racemization method of the present invention can be preferably applied, mention can be made of phenylalanine, substituted phenylalanine, leucine, alanine and methionine, preferably phenylalanine, 4-chlorophenylalanine and leucine.
[0020] In the present invention, α-amino acid is not specifically restricted with respect to its stereo-structure if the α-amino acid has an optical activity. It is possible to employ not only an optically active α-amino acid such as D-α-amino acid and L-α-amino acid but also an α-amino acid mixture having optical activity wherein any one of D-α-amino acid and L-α-amino acid is present in excess or predominantly.
[0021] In the context of the present invention, therefore, the term “an optically active α-amino acid” means any one of D-α-amino acids and L-α-amino acids, and the term “α-amino acid (mixture) having optical activity” means not only an optically active α-amino acid such as D-α-amino acid or L-α-amino acid but also a mixture of α-amino acid stereoisomers, wherein said mixture has an optical activity since any one of D-α-amino acid and L-α-amino acid is present in excess or predominantly. But said terms are not strictly employed.
[0022] In the present invention, the phase transfer catalyst can be selected from a quaternary ammonium salt of general formula R4N+X− or quaternary phosphonium salt of general formula of R4P+X−, wherein R independently represents an alkyl group having 1˜20 carbon atoms, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group, and X represents Cl, Br, I or OH. For example, mention can be made of tetrabutylammonium chloride, cetyl trimethylammonium bromide, benzyl trimethylammonium chloride, Aliquat 336 (commercial name), tetraphenylphosphonium hydroxide, or the like.
[0023] According to a preferred embodiment of the present invention, the phase transfer catalyst is selected from tetraalkylammonium halides, and specifically, mention can be made of Aliquat 336.
[0024] According to one embodiment of the present invention, the racemization method of the α-amino acid may specifically comprise the following steps:
(A) preparing an organic phase containing the above copper metal complex of the chemical formula (1) and the above phase transfer catalyst, (B) preparing a basic aqueous phase comprising an optically active α-amino acid and an alkaline compound, (C) vigorously stirring a two-phase mixture obtained by combining the organic phase and the aqueous phase at a temperature 10 to 80° C., specifically at 20 to 70° C., preferably 30 to 60° C. for 1 to 40 hours, specifically 2 to 35 hours, preferably 3 to 30 hours, (D) optionally, separating the racemized amino acid from the aqueous phase separated in a layer, (E) optionally, allowing the above-resultant two-phase mixture to stand to separate an organic phase and an aqueous phase into layers, (F) optionally, employing the organic phase separated in a layer again in step (a).
[0031] According to yet another embodiment of the invention, the racemization method of α-amino acids can comprise (1) a step for preparing an organic phase comprising a copper metal catalyst [step (A)], (2) steps for carrying out a racemization of optically active α-amino acid [steps (B) and (C)], (3) steps for recovering the racemized α-amino acid [steps (D) and (E)], and (4) a step for recycling the racemization catalyst [step (F)].
[0032] Below, detailed descriptions are provided for the step (1) for preparing an organic phase containing a catalyst of copper metal complex [Step (A)], and for the step (2) of carrying out a racemization of an optical active α-amino acid [Steps (B) and (C)].
[0033] (1) Preparation of a Catalyst of Copper Metal Complex and an Organic Phase Comprising the Same
[0034] According to a preferred embodiment of the present invention, an organic phase comprising the above copper metal complex and the above phase transfer catalyst can be obtained by the method comprising the following steps:
(a-1) preparing an organic phase comprising salicylaldehyde and a phase transfer catalyst, (a-2) preparing a basic aqueous phase comprising α-amino acid, an alkali compound and a copper salt compound, (a-3) stirring a two-phase mixture of the organic phase and the aqueous phase, (a-4) allowing the resultant two-phase mixture to stand to separate an organic phase into a layer.
[0039] First, in step (a-1), an organic phase is prepared by adding salicylaldehyde or its derivative (e.g., 5-nitrosalicylaldehyde) and a phase transfer catalyst (e.g. Aliquat 336) into an organic solvent such as dichloromethane (CH2Cl2).
[0040] In step (a-2), a basic aqueous phase is prepared by dissolving an optically active α-amino acid and/or a racemic α-amino acid (e.g. phenylalanine) in distilled water; adding sodium hydroxide into the resultant aqueous solution to make it alkaline; and adding a copper salt compound into the resultant basic aqueous solution.
[0041] In step (a-3), a two-phase mixture of the above organic phase and the above basic aqueous phase is stirred to contact the organic phase and the aqueous phase, so that the amino acid and copper ion are transferred into the organic phase by the phase transfer catalyst. Then, in the organic phase, salicylaldehyde, amino acid and copper ions will form a Schiff base according to the process shown in Scheme 1, and then form a copper metal complex.
[0042] In step (a-4), the resultant two-phase mixture is allowed to stand so that a layer separation of an aqueous phase and an organic phase occurs, and then the organic layer is separated, for example, by using a separating funnel. Since the resultant organic phase contains copper metal complex of Formula 1 and a phase transfer catalyst, it will be used as “an organic phase containing a catalyst of copper metal complex” in the next racemization step.
[0043] Organic solvents which can be used for an organic phase in the step for forming a copper metal complex is not particularly limited, but mention can be made of, for example, dichloromethane, dichloroethane and chloroform.
[0044] As examples of the alkali compound, mention can be made of an alkali metal hydroxide or alkaline earth metal hydroxide, specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide. The amount of the alkali compound is not particularly limited, but it may be added in an amount of 0.9 to 2.0 equivalents, specifically 0.9 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents, with respect to the α-amino acid.
[0045] As a source of copper ions, it is possible to use a variety of copper salts, and mention can be specifically made of copper salt compounds containing divalent copper ion, for example, copper chloride (CuCl2), copper sulfate (CuSO4), copper acetate (Cu(OAc)2), or the like.
[0046] (2) Racemization of an Optical Active α-Amino Acid
[0047] The racemization of an optically active α-amino acid can be carried out by contacting an organic phase [prepared in step (A)] containing copper metal complexes and the above-described phase transfer catalyst with a basic aqueous phase [prepared in Step (B)] containing an optically active α-amino acid and an alkali compound.
[0048] In the above step (B), the basic aqueous phase can be prepared by adding α-amino acid and an alkali compound such as sodium hydroxide into water. α-Amino acids can be used in an amount of 1 to 50 equivalents, in particular 2 to 30 equivalents, preferably 5 to 20 equivalents with respect to salicylaldehyde derivatives of the above organic phase, and the alkali compound can be added in an amount of 0.9 to 2.0 equivalents, specifically 0.9 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents with respect to α-amino acid.
[0049] In the above step (C), the contact of an aqueous phase and an organic phase can be carried out by combining the aqueous phase and the organic phase to form a two-phase mixture, which is then stirred at or around the normal temperature, generally at a temperature of 10 to 80 ° C., specifically 20 to 70 ° C., preferably 30 to 60 ° C. for a period of 1 to 40 hours, specifically 2 to 35 hours, preferably 3 to 30 hours. If the reaction temperature is high, the copper metal complex may be slightly decomposed to reduce the racemization velocity. If the reaction temperature is low, there is a tendency the racemization velocity decreases.
[0050] In said step (D), when the resultant two-phase mixture is allowed to stand, the organic phase and the aqueous phase are separated and each of them can be obtained by using a separating funnel or the like. From the resultant aqueous phase, the racemized amino acid can be isolated and purified. The resultant organic phase can be recycled as a racemization catalyst, specifically reused as an organic phase in the above step (A). In such case, it is possible to further add the catalyst of copper metal complex and/or the phase transfer catalyst, if necessary. It has been confirmed that, according to the present invention, an organic phase containing the catalyst of copper metal complex can maintain its catalytic activity even after use in at least 5 times of racemization.
[0051] As organic solvents that can be employed as the organic phase in the racemization step, mention can be made of organic solvents which have been employed as an organic phase in the manufacturing step of copper metal complex, and preferably of dichloromethane.
[0052] According to the present invention, since the racemization of α-amino acid can be carried out under mild conditions, the decomposition of α-amino acid hardly occurs, and accordingly the yield of α-amino acid is high. In addition, since the organic phase is separated from the aqueous phase after the completion of racemization of α-amino acid, the organic phase containing copper metal complex can be reused at least 5 times without a decrease of catalytic activity. Since the aqueous phase containing racemized α-amino acid almost does not contain copper metal complex, copper ions and salicylaldehyde or the like, it is easy to isolate and purify α-amino acid. Therefore, according to the present invention, it is possible to economically perform the racemization of an optically active α-amino acid on a large scale.
[0053] Below, the present invention will be described in detail by examples. However, the examples are given for the purpose of illustrating the invention in more detail and do not restrict the scope of the present invention. The following examples can be appropriately modified or altered by a skilled person having an ordinary knowledge within the scope of the invention.
EXAMPLE 1
Racemization of L-phenylalanine
[0054] (1) Preparation of an Organic Layer Containing Copper Metal Complex
[0055] In dichloromethane 120 mL, 5-nitrosalicylaldehyde (10.0 g, 59.8 mmol) and Aliquat 336 (33.9 g, 83.9 mmol) were dissolved to give an organic phase. In distilled water 100 ml, racemic phenylalanine (19.8 g, 119.9 mmol), sodium hydroxide (5.75 g, 144 mmol) and copper chloride (CuCl2) (1.6 g, 11.9 mmol) were dissolved to give an aqueous phase. The organic phase and the aqueous phase were mixed, the resultant two-phase mixture was vigorously stirred for 2 hours, followed by a phase separation to give an organic layer containing copper metal complex.
[0056] (2) Racemization
[0057] In distilled water 500 ml, L-phenylalanine (98.8 g, 598 mmol) and sodium hydroxide (28.7 g, 718 mmol) were dissolved to give an aqueous phase, to which the organic layer obtained in the above step 1) was introduced. The resultant two-phase mixture was stirred at 25° C. for 12 hours, followed by a phase separation to give an aqueous layer. The aqueous layer was analyzed with a chiral column (Chirosil RCA) and it was confirmed that L/D ratio of phenylalanine is 50.2/49.8 and thus a racemization has occurred.
[0058] Conditions for the Chiral HPLC Analysis
Column: Chirosil RCA 5 uM×25 Cm Mobile phase: 10 mM HClO4 50% in MeOH Velocity of mobile phase: 0.5 mL/min Column temperature: 40° C.
Examples 2˜5
Racemization of L-phenylalanine
[0063] In the same manner as in Example 1, step 1) and step 2) were performed to proceed a racemization of phenylalanine.
[0064] The racemization results of Examples 1-5 are shown in Table 1 below:
[0000]
TABLE 1
Examples
Reaction time
L/D ratio
1
12 h
50.1/49.8
2
12 h
50.1/49.9
3
16 h
50.0/50.0
4
15 h
51.5/45.5
5
16 h
51.0/49.0
Example 6
Racemization of L-phenylalanine
[0065] 1) Preparation of an Organic Layer Containing Copper Metal Complex
[0066] In dichloromethane 70 mL, 5-nitrosalicylaldehyde (5.0 g) and Aliquat 336 (17 g) were dissolved to give an organic phase. In distilled water 50 ml, L-phenylalanine (10 g), sodium hydroxide (2.9 g) and copper chloride (CuCl2) (0.8 g) were dissolved to give an aqueous phase. The organic phase and the aqueous phase were mixed and the resultant two-phase mixture was vigorously stirred for 2 hours, followed by a phase separation to obtain an organic layer containing copper metal complex.
[0067] 2) Racemization
[0068] In distilled water 260 ml, L-phenylalanine (50 g) and sodium hydroxide (14.5 g) were dissolved to give an aqueous phase, to which the organic layer obtained in the above step 1) was introduced. The resultant two-phase mixture was stirred at 25° C. for 12 hours, followed by a phase separation to give an aqueous layer. The aqueous layer was analyzed with a chiral column (Chirosil RCA) and it was confirmed that a racemization has occurred.
Example 7
Racemization of L-phenylalanine
[0069] 1) Preparation of an Organic Layer Containing Copper Metal Complex
[0070] In dichloromethane 115 mL, salicylaldehyde (7.3 g) and Aliquat 336 (33.6 g) were dissolved to give an organic phase. In distilled water 100 ml, racemic phenylalanine (19.8 g), sodium hydroxide (5.75 g) and copper sulfate (CuSO4) (1.9 g) were dissolved to give an aqueous phase. The organic phase and the aqueous phase were mixed and the resultant two-phase mixture was vigorously stirred for 2.5 hours, followed by a phase separation to obtain an organic layer containing copper metal complex.
[0071] 2) Racemization
[0072] In distilled water 500 ml, L-phenylalanine (98.8 g) and sodium hydroxide (28.7 g) were dissolved to prepare an aqueous phase, to which the organic phase obtained in the above step 1) was added. The resultant two-phase mixture was stirred for 13 hours at 25° C., followed by phase separation to give an aqueous layer. The aqueous layer was analyzed by a chiral column (Chirosil RCA) and it was confirmed that L/D ratio of phenylalanine is 50.8/49.2 and thus a racemization has occurred.
Example 8
Racemization of L-4-chlorophenylalanine
[0073] 1) Preparation of an Organic Layer Containing Copper Metal Complex
[0074] In dichloromethane 130 mL, 5-nitrosalicylaldehyde (10.0 g) and Aliquat 336 (33.9 g) were dissolved to prepare an organic phase. In distilled water 150 ml, racemic 4-chlorophenylalanine (24.0 g), sodium hydroxide (5.77 g) and copper chloride (CuCl2) (1.4 g) were dissolved to prepare an aqueous phase. The organic phase and the aqueous phase were mixed and the resultant two-phase mixture was vigorously stirred for 2 hours, followed by phase separation to obtain an organic layer containing copper metal complex.
[0075] 2) Racemization
[0076] In distilled water 700 ml, L-4-chlorophenylalanine (120 g) and sodium hydroxide (28.0 g) were dissolved to prepare an aqueous phase, to which the organic layer obtained in the above step 1) was added. The resultant two-phase mixture was stirred at 30° C. for 13 hours, followed by phase separation to give an aqueous layer. The aqueous layer was analyzed by a chiral column (Chirosil RCA) and it was confirmed that L/D ratio of 4-chlorophenylalanine is 50.1/49.9 and thus a racemization has occurred.
[0077] Conditions for the Chiral HPLC Analysis
Column: Chirosil RCA Mobile phase: 10 mM HClO4 50% in MeOH Velocity of mobile phase: 0.5 mL/min Column temperature: 40° C.
Examples 9˜10
Racemization of L-4-chlorophenylalanine
[0082] In the same manner as in Example 8, step 1) and step 2) were performed to proceed a racemization of L-4-chlorophenylalanine.
[0083] The racemization results of Examples 8˜10 are shown in Table 2 below:
[0000]
TABLE 2
Examples
Reaction time
L/D ratio
8
13 h
50.1/49.9
9
15 h
50.0/50.0
10
15 h
51.1/48.9
Example 11
Racemization of L-leucine
[0084] 1) Preparation of an Organic Layer Containing Copper Metal Complex
[0085] In dichloromethane 40 mL, 5-nitrosalicylaldehyde (3.4 g) and Aliquat 336 (12 g) were dissolved to give an organic phase. In distilled water 40 ml, racemic leucine (5.2 g), sodium hydroxide (1.75 g) and copper chloride (CuCl2) (0.6 g) were dissolved to give an aqueous phase. The organic phase and the aqueous phase were mixed and the resultant two-phase mixture was vigorously stirred for 1 hour, followed by a phase separation to obtain an organic layer containing copper metal complex.
[0086] 2) Racemization
[0087] In distilled water 100 ml, L-leucine (13.3 g) and sodium hydroxide (4.8 g) were dissolved to prepare an aqueous phase, to which the organic layer obtained in the above step 1) was added. The resultant two-phase mixture was stirred at 35° C. for 15 hours, followed by phase separation to give an aqueous layer. The aqueous layer was analyzed by a chiral column (Sumichiral OA-5000) and it was confirmed that L/D ratio of leucine is 51.0/49.0 and thus a racemization has been carried out.
[0088] Conditions for the Chiral HPLC Analysis
Column: Sumichiral OA-5000 Mobile phase: 10% ACN in 2 mM CuSO4 Velocity of mobile phase: 1.0 mL/min Column temperature: 30° C.
INDUSTRIAL APPLICABILITY
[0093] The method of the present invention can be industrially utilized in the production of an optically active α-amino acid which can be used as a raw material or intermediate in the field of pharmaceuticals, agriculture and fine chemistry.
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According to the present invention, a method is provided wherein a basic aqueous phase containing an optically active α-amino acid is brought into contact with an organic phase containing a racemisation catalyst in the form of a copper metal complex of copper ions and an α-amino acid and salicylaldehyde, in the presence of a phase transition catalyst, thereby subjecting the optically active α-amino acid to racemisation. In the α-amino acid racemisation method according to the present invention, the reaction conditions are mild and thus there is little α-amino acid breakdown and the yield is high, the racemisation catalyst can be reused, the α-amino acid resulting from the racemisation can easily be isolated and purified, and the racemisation method can be implemented in volume such that the invention is economic.
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BACKGROUND OF THE INVENTION
The present invention relates to a color separating optical apparatus which is capable of reading color-separated picture signals using a single light-receiving means.
Conventional types of apparatus contemplated by the present invention include color copying machines, color scanners, etc. The optical system of these apparatus is basically composed of a light source for illuminating the object, an imaging lens unit for focusing reflected light from the object on a light-receiving means such as a CCD or a photoreceptor drum, and a plurality of color-separating filters having different wavelength selection characteristics, which are inserted into the optical path for detecting plural pieces of color information using a single light receiving means.
In this type of apparatus, the color information on the object is color-separated on the basis of the brightness of each of the three primary colors, which necessitates receiving the reflected light from the object several times, with an appropriate filter being selected. The pieces of color-separated information are superposed to produce an output color picture that reproduces the color information of the object.
A problem with the apparatus described above is that the overall spectral characteristics of the system which are determined by the characteristics of the light source and the spectral sensitivity of the light-receiving means are not flat, so that different energies are produced for different colors. This results in the failure to perform effective control of color reproduction since the density of the output color picture will vary from one color to another.
SUMMARY OF THE INVENTION
The present invention solves the aforementioned problems of the prior art. An object of this invention is to provide a color separating optical apparatus that is capable of eliminating the difference between the quantities of output energy for each of the separated colors, produced on account of the overall spectral characteristics of the system.
In order to attain this object, the present invention provides a color separating optical apparatus that comprises an imaging lens unit that allows the reflected light from the object as illuminated with a light source to focus on a light-receiving means disposed at a position generally conjugate to the object, a plurality of color-separating filters which are selectively inserted into the optical path extending from the object to the light-receiving means and which respectively limit the wavelength of the light in such a way that it will reach the light-receiving means at wavelengths in different ranges, and a plurality of light-shielding means that are selectively inserted in the optical path to adjust the quantity of light transmission. In the present invention, the light-shielding means are selected in accordance with the selection of the color-separating filter so as to eliminate the differences between the output energies of each of the separated colors produced on account of the spectral characteristics of the light source and the light-receiving means.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic drawing of a color copying machine according to a first embodiment of the color separating optical apparatus of the present invention;
FIG. 2 is a plan view of the filter unit in the apparatus shown in FIG. 1, as seen from direction defined by line II--II in FIG. 1;
FIG. 3 is a diagram showing the transmission characteristics of the color separating filters;
FIG. 4 is a diagram showing the spectral characteristics of the light source and light-receiving means employed in the apparatus shown in FIG. 1;
FIG. 5 is a diagram showing the spectral characteristics of the apparatus shown in FIG. 1 when not furnished with light shields;
FIG. 6 is a schematic drawing showing a modification of the apparatus shown in FIG. 1;
FIG. 7 is a plan view of the filter unit shown in FIG. 6;
FIG. 8 is a schematic drawing showing the essential parts of a color scanner according to a second embodiment of the color separating optical apparatus of the present invention;
FIG. 9 is a diagram of the spectral characteristics of the light source and the light-receiving means employed in the apparatus shown in FIG. 8;
FIG. 10 is a diagram showing the spectral characteristics of the apparatus shown in FIG. 8 when not furnished with light shields;
FIG. 11 is a plan view of the filter unit in the apparatus shown in FIG. 8, as seen from the direction defined by line XI--XI in FIG. 8.
FIG. 12 is a block diagram showing the composition of a light source usable in the apparatus shown in FIG. 1;
FIG. 13 is a plan view of the filter unit in the apparatus shown in FIG. 1;
FIG. 14 is a diagram showing the transmission characteristics of a filter for the R component;
FIG. 15 is a diagram showing the transmission characteristics of a filter for the G component;
FIG. 16 is a diagram showing the transmission characteristics of a filter for the B component;
FIG. 17 is a diagram showing the transmission characteristics of an ND coating layer; and
FIG. 18 is a diagram showing the transmission characteristics of a filter for the R component which is coated with an ND layer.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is described hereinafter with reference to the accompanying drawings.
FIG. 1 shows schematically the optical system of a color copying machine according to a first embodiment of the color-separating optical apparatus of the present invention.
The optical system shown in FIG. 1 is chiefly intended to copy, on a different sheet of paper (not shown), a document 20 placed as the object on a contact glass 10. As shown, the system is generally composed of a halogen lamp 30 which is a light source for illuminating the document 20, first to fourth mirrors 40, 41, 42 and 43 which guide the reflected light from the document 20 illuminated with the halogen lamp 30, an imaging lens unit 60 which is disposed between the second and third mirrors to form an image of the document on a photoreceptor drum 50 serving as a light-receiving means, and a filter unit 70 disposed behind but in proximity to the imaging lens unit 60.
As shown in FIG. 2, the filter unit 70 has three color-separating filters 71, 72 and 73 for detecting information on the three primary colors (R, red; G, green; B, blue). The spectral transmission characteristics of the respective filters are as shown in FIG. 3. For reasons to be explained later the color separating filters 71 and 72 are equipped with masks 71a and 72a (as indicated by hatched areas in FIG. 2) which: serve as light-shielding means for limiting the cross-sectional area of the transmitted light.
The system shown in FIG. 1 is designed so that the light reflected from the document 20 is guided by the mirrors, filters and lenses to perform slit exposure on the photoreceptor drum 50. When reading the document, the halogen lamp 30 and the first and second mirrors 40 and 41 scan in the direction indicated by the arrows and the information associated with each scanning position is continuously read onto the photoreceptor drum 50.
The light issuing from the halogen lamp 30 employed in this apparatus has spectral characteristics characterized by an increase in energy toward the longer wavelengths. In contrast, the photoreceptor on the drum 50 has a spectral sensitivity curve which has a peak at about 550 nm as shown by the broken line in FIG. 4. Therefore, the overall spectral characteristics of the system are not flat but have an increasing gradient toward the longer wavelengths.
If color separating filters having the characteristics shown in FIG. 3 are selectively inserted into the optical path in such a way that the information from the document 20 is color-separated using light beams whose luminous flux has the same cross-sectional area for each color, even areas on the document 20 having the same level of luminance will produce energy whose amount varies with color as shown in FIG. 5. If, in the example shown, the output energy of the B component is assumed to be 100, the G and R components will produce outputs of 111 and 386, respectively, for the same input energy level. Therefore, if not corrected, a hard copy will be obtained in which blues are reproduced faithfully but in which vermilion or other shades of red have produced unclear images.
In order to avoid this problem, as already stated, the color separating filters 71 and 72 in the filter unit 70 are furnished with masks 71a and 72a as light shields, and the diameter of each mask is adjusted so that the cross-sectional area of the luminous flux of the light beams passing through the associated filter provides a ratio of 100/111 for the G component and 100/386 for the R component, with the value for B component being assumed to be 100.
The operation of the color copier described above proceeds as follows. First, the color separating filter 71 for the R component in the filter unit 70 is inserted into the optical path and at the same time, the surface of the photoreceptor drum 50 is positively charged by corona discharge using a charger (not shown).
In the next step, the halogen lamp 30 is lit and remains illuminated as it is slid beneath the contact glass 10 together with the first and second mirrors 40 and 41. The light reflected from the document 20 is guided by the first and second mirrors 40 and 41, passes through the color separating filter 71 for the R component, and emerges therefrom as a light beam carrying only that information related to the R component. As a result of passage through the filter 71, the light has its cross-sectional area (luminous flux) reduced by the mask 71a.
The light emerging from the lens unit 60 passes through the filter unit 70 and is reflected by the third and fourth mirrors 42 and 43 to perform slit exposure on the photoreceptor drum 50. Note, however, that filter unit 70 can also be positioned before the lens unit 60. Since the electrical resistance of the photoreceptor layer on the drum 50 varies with the intensity of light, the positive charges on the intensely illuminated areas will disappear and those in the weakly illuminated areas will remain intact, thereby forming a latent electrostatic image on the surface of the drum 50 in a pattern corresponding to the amount of R component exposure. The particles of a toner of a cyan color which is complementary, to the R component are then deposited on the latent image and the resulting toner image is transferred to paper by corona discharge. As a result, only the image of the cyan color which is complementary to the R component is formed on the copy paper.
Thereafter, the filter unit 70 is shifted in a direction normal to the paper of FIG. 1 and the color separating filter 72 for the G component is inserted into the optical path. By repeating the same procedure as described in the preceding paragraph, a latent electrostatic image is formed on the photoreceptor drum 50 in a pattern corresponding to the amount of G component exposure. As light beams pass through the filter 72, the cross-sectional area of the luminous flux is restricted to a predetermined value by the mask 72a.
Particles of a toner of magenta color, which is complementary to the G component, are deposited on the latent image and the resulting toner image is transferred to the paper in registry with the previously formed cyan toner image. As a result, both the cyan image, which is complementary to the R component, and the magenta image, which is complementary to the G component, are formed on the copy paper.
Thereafter, the filter 73 for the B component is inserted into the optical path and the above-described procedures are repeated to form an image of a yellow color which is complementary to the B component, and this image is superposed on the two previously formed toner images. As a result, the three colors cyan, magenta and yellow, are superposed in registry to reproduce the information of the document 20 on the copy paper.
In the final step, the superposed images are fixed and the copy paper emerges from the machine.
As described above, in accordance with the present invention, the cross-sectional area of the luminous flux of light is adjusted to match the specific color whose information is to be detected. By so doing, the difference in the quantity of output energy with color that is produced on account of the overall. spectral characteristics of the system can be sufficiently suppressed to provide improved color reproduction. In this connection, it should be mentioned that the filter unit 70 may be inserted in the optical path behind the imaging lens unit 60, rather than in front of it as in the embodiment described above.
FIG. 6 shows a modification of the first embodiment of the present invention, in which a filter unit 80 designed as shown in FIG. 7 is disposed at a position corresponding to a diaphragm stop in the opening between the two outermost surfaces of the imaging lens unit 60. This filter unit 80 has three color-separating filters 81, 82 and 83 which perform the same functions as those described in connection with the first embodiment, except that each of the masks 81a and 82a serving as a light shield is in the form of a circle whose center is in alignment with the optical axis of the imaging lens unit 60.
The circular masks 81a and 82a offer the following advantages: they serve as diaphragm stops to increase the depth of focus during the reading of information related to the R and G components, and the effects of axial chromatic aberration occurring in the optical system can be sufficiently reduced to provide improved imaging performance.
FIG. 8 schematically shows essential parts of the optical system in a color scanner according to a second embodiment of the color separating optical apparatus of the present invention.
In this optical system, the light reflected from a document 90 illuminated with a light source (not shown) is guided through a filter unit 100 and an imaging lens unit 110 which focuses an image on CCD 120 serving as a light-receiving means.
The fluorescent lamp which is used as the light source in this system has spectral characteristics as shown by the solid line in FIG. 9, and the CCD 120 has a spectral sensitivity curve as shown by the broken line in the same drawing. Therefore, as in the case of the first embodiment, the overall spectral characteristics of the system have an increasing gradient toward the longer (red) wavelengths.
If color separating filters having the characteristics shown in FIG. 3 are selectively inserted into the optical path in such a way that the information in the document 90 is color-separated using light beams whose luminous flux has the same cross-sectional area for each color, areas on the document 90 having the same level of luminance will produce energy whose amount varies with color as shown in FIG. 10. If, in the example shown, the output energy of the B component is assumed to be 100, the G and R components will produce outputs of 114 and 144, respectively, for the same input level of energy.
In order to ensure that uniform energy will be produced from the colors obtained by color separation, the apparatus under consideration employs color separating filters 101, 102 and 103 which, as shown in FIG. 11, are furnished with masks 101a, 102a and 103a on their respective surfaces, and the diameter of each mask is adjusted so that the cross-sectional area of the luminous flux of the light passing through the associated filter provides a ratio of 100/114 for the G component and 100/144 for the R component, with the value for the B component being assumed to be 100.
Each of the masks used in the second embodiment is designed so that it will block the central portion of the incident light beam in a greater amount than the peripheral edge. In other words, by achieving a relative improvement in the brightness of the edge of the image field, an unevenness in the quantity of light that would otherwise occur at the CCD 120 because of the cosine-fourth-power law is suppressed.
In the first and second embodiments of the present invention described above, the light shields are attached as masks on the surface of the associated color separating filters. Needless to say, the light shields may be provided as members separate from the filters although it becomes necessary to provide separate means for moving the light shields in addition to the means for moving the filters.
Instead of masks which adjust the cross-sectional area of the luminous flux of the incident light, ND (neutral density) filters having different transmittances may be employed as a means for changing the output energy for each color.
A further embodiment of the invention is shown in FIG. 12, which illustrates an alternative light source which is usable with the system structure shown in FIG. 1.
As shown in FIG. 12, the light source comprises two halogen lamps 30 and 31, and a switching circuit SC which allows either one or both of these halogen lamps to be lit as required in the scanning mode to be described below. The switching circuit SC is controlled by a one-bit signal from a central control circuit CC which controls the entire system of the copier in such aspects as scanning and filter selection.
As shown in FIG. 13, the filter unit 70 has three color-separating filters 71, 72 and 73 for detecting information in the three primary colors. These filters are selectively inserted into the optical path in response to a signal supplied from the central control circuit CC.
FIGS. 14-16 show the spectral transmission characteristics of the color-separating filters; FIG. 14 shows the characteristics of the filter 71 for the R component, FIG. 15, the filter 72 for the G component, and FIG. 16, the filter 73 for the B component. For the reasons described below, the filter 71 for the R component is coated with a neutral density (ND) layer having a transmittance of 70% (see FIG. 17) which reduces uniformly the energy of the incident luminous flux over the entire region of its cross section. FIG. 18 shows the spectral transmission characteristics of the filter 71 coated with this ND layer.
The system shown in FIG. 1 is designed so that the light reflected from the document 20 is guided by the mirrors, filters and lenses to perform slit exposure on the photoreceptor drum 50. When reading the document, the halogen lamps 30 and 31 of this embodiment and the first and second mirrors 40 and 41 scan in the direction indicated by arrows in FIG. 1 and the information associated with each scanning position is continuously read onto the photoreceptor drum 50.
The light issuing from the halogen lamps employed in this embodiment has spectral characteristics which, as shown by a solid line in FIG. 4, are characterized by an increase in energy toward the longer wavelength side. In contrast, the photoreceptor on the drum 50 has a spectral sensitivity curve which has a peak at about 550 nm as shown by a broken line in FIG. 4. Therefore, the overall spectral characteristics of the system are not flat but have an increasing gradient toward the longer wavelength side.
If color separating filters having the characteristics shown in FIGS. 14-16 are selectively inserted into the optical path without adopting any other means for limiting the energy for each color, areas on the document 20 having the same level of luminance will produce energy whose amount varies with color as shown in FIG. 5. Therefore, if no countermeasures are taken, a hard copy will be obtained in which blues are reproduced faithfully but which fails to produce a clear image in vermilion or other shades of red.
In order to avoid this problem, the switching circuit SC in the system of the present invention allows both halogen lamps 30 and 31 to be lit when light in the range of low spectral sensitivity is being received (i.e., when the filter 73 for the B component is selected), whereas it allows only one of the halogen lamps to be lit when light in the range of higher spectral sensitivity is being received (i.e., when the filters 71 and 72 for the G and the R components are selected). Furthermore, the energy of the luminous flux passing through the filter 71 for the R component is reduced by an ND layer coated on that filter. As a result of the combination of these effects, the output energy from the reception of light of the B component is increased whereas the output energy from the reception of light of the R component is reduced, and each of these energy outputs can be made equal to that produced when light of the G component is received, thereby allowing a substantially uniform output level to be maintained for each of the three components R, G and B.
The operation of the color copier described above proceeds as follows. First, the filter 71 for the R component in the filter unit 70 is inserted into the optical path and at the same time, the surface of the photoreceptor drum 50 is positively charged by corona discharge with a charger (not shown).
In the next step, only halogen lamp 30 is lit and continues to be illuminated as it is slid beneath the contact glass 10 together with the first and second mirrors 40 and 41. The light reflected from the document 20 is guided by the first and second mirrors 40 and 41, passes through the imaging lens unit 60, passes through the filter 71 for the R component, and emerges therefrom as light beams carrying only the information related to the R component. In this case, by the action of the ND layer coated on the filter 71, the energy of the luminous flux of the light passing through that filter is uniformly reduced over the entire region of its cross section.
The light emerging from the filter unit 70 and is reflected by the third and fourth mirrors 42 and 43 to perform slit exposure on the photoreceptor drum 50. Again, the filter unit 70 may be positioned before the lens unit 60. Since the electrical resistance of the photoreceptor layer on the drum 50 varies with the intensity of light, the positive charges on the intensely illuminated areas will disappear and those in the weakly illuminated areas will remain intact, thereby forming a latent electrostatic image on the surface of the drum 50 in a pattern corresponding to the amount of exposure. Toner of cyan color is then deposited on the latent image and the resulting toner image is transferred to copy paper by corona discharge.
Thereafter, the filter unit 70 is shifted in a direction normal to the paper of FIG. 1 and the color separating filter 72 for the G component is inserted into the optical path. By repeating the same procedures as described in the preceding paragraph and with only halogen lamp 30 kept lit, a latent electrostatic image is formed on the photoreceptor drum 50 in a pattern corresponding to the G component exposure.
Toner of magenta color is deposited on the latent image and the resulting toner image is transferred to the paper in registry with the toner image already formed. As a result, both the cyan image and the magenta image are formed on the copy paper.
Thereafter, the filter 73 for the B component is inserted into the optical path and scanning is performed with both halogen lamps 30 and 31 kept lit, so as to form a latent electrostatic image in a pattern corresponding to the amount of B component exposure. Toner of a yellow color is deposited on this latent image, with the resulting toner image being transferred to the paper, so that the three colors cyan, magenta and yellow, are superposed in registry to reproduce the information of the document 20 on the copy paper.
In the final step, the superposed images are fixed and the copy paper emerges from the machine.
The amount of exposing light and the transmission characteristics of the filters may be adjusted to match the specific color whose information is to be detected. By so doing, the difference in the quantity of output energy with color that is produced on account of the overall spectral characteristics of the system can be sufficiently suppressed to provide improved color reproduction.
In the embodiment just described, the amount of exposing light is adjusted and an ND layer is coated only on the filter for the R component. If desired, ND layers having different transmittances may be coated on the filters for the R and G components, with the amount of exposing light being held constant. In this alternative case, exposing light cannot be utilized as effectively as in the first case because the transmittance of the filter for the R component must be held at a considerably low level in order to adjust the level of the energy of the received light of the R component to that of the energy of the B component.
The embodiments described above concern the case where the concept of the present invention is applied to an apparatus having greater sensitivity in the longer wavelength range. It should, however, be noted the concept of the present invention is also applicable to an apparatus having greater sensitivity in the shorter wavelength range, provided that measures similar to those described above are employed, such as the use of an energy attenuating layer on the surface of the filter for the B component.
As described in the foregoing, the present invention ensures that nonuniformity that would otherwise be introduced into the correspondence between color and output energy due to the overall spectral characteristics of the system can be substantially eliminated by adopting one of the optical arrangements specified herein, including coating the surface of a color separating filter with an energy-attenuating layer that reduces the energy of the luminous flux in a manner not specific to wavelength. Furthermore, this attenuating layer allows the energy to be uniformly reduced over the entire region of its cross section, so that the balance in the distribution of light within a picture will not be upset even if the associated filter is disposed at a position that may affect imaging performance.
The above-described feature of the present invention may be combined with an adjustment in the amount of exposing light. In this case, the output energy of the light in the range of low spectral sensitivity is increased whereas the output energy of the light in the range of higher spectral sensitivity is reduced so as to adjust the two levels of output energy to that of light in the intermediate sensitivity range. By so doing, one is capable of avoiding an undue decrease in the energy of received light that world otherwise result from the use of an attenuating layer having low transmittance.
If light shields having a circular opening are disposed at a position corresponding to a diaphragm stop in the aperture of an imaging lens unit, the effects of axial chromatic aberration can be sufficiently reduced by the diaphragm effect to provide improved imaging performance.
If light shields are designed to block the central part of the incident light beams in a greater amount than at the peripheral edge thereof, they are made capable of reducing unevenness in the quantity of light that would otherwise occur at the light-receiving means on account of the operation of cosine-fourth-power law.
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A color separating optical apparatus is provided with a compensating members in order to compensate for the differences in output energy of the separated colors which is attributable to the particular spectral characteristics of the light source and the light receiver. In various embodiments, selectable masks are used to control the light flux, or the light source itself is controlled as to the number of lamps energized for each color.
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BACKGROUND OF THE INVENTION
This invention relates to compositions of matter comprising polydentate ligand complexes of chromium, vanadium and titanium having an electrochemically generated 2+ formal valence charge on the metal atom in the complex, processes for their formation, processes for their use as reducing agents in bleaching or brightening lignocellulosic pulps, principally wood pulp, either as mechanical wood pulp, or chemical wood pulp and to the brightened pulps produced thereby.
Reductive bleaching or brightening of lignocellulosic pulps particularly mechanical wood pulps has long been practiced. The principal reagent for this purpose has been hydrosulfite (dithionite) ion (S 2 O 4 = ) exployed principally as its zinc or sodium salts in aqueous solution. More recently sodium borohydride (NaBH 4 ) in various formulations has also been employed as a replacement for hydrosulfite.
The problems and limitations involved in the use of both reagents, such as, lack of stability in solution or in the presence of oxygen, the inability to reuse spent reagent requiring its environmentally acceptable disposal and the limited ability of either reagent to produce high brightness pulp are well known to those skilled in the art.
Applicants have discovered a new series of reducing agents which are capable of eliminating or minimizing most of the deficiencies of borohydride and hydrosulfite in reductive bleaching of lignocellulosic pulp.
The use of reducing agents generated electrochemically, particularly of reducing agents generated electrochemically in situ in the process, to reductively bleach lignocellulosic pulp does not appear to have been suggested in the prior art.
Discussion of Relevant art
Fleury and Rapson in their Article "Characterization of Chromophoric Groups in Groundwood and Lignin Model Compounds by Reaction with Specific Reducing Agents", Technical Paper T154, Pulp and Paper Magazine of Canada, Mar. 15, 1968, pp. 62 to 68 described experiments intended to assist in characterizing the fundamental structure of lignin. As part of this study uranium III and chromium II in acidic aqueous solution were employed to reduce model lignin chromophores and groundwood lignin. Dithionite and borohydride were also compared and among the results noted was that the aquo-uranium III cation was a powerful reducing agent and reduced groundwood to a higher brightness level than dithionite. It was also noted in the article that because of the heterogenous nature of the groundwood lignin reduction and the fact that the reduction took place outside the aqueous solution, the reduction potential in water would not be a good predictor of activity in brightening lignin in wood and results from one successful reductant could not be applied universally. Fleury and Rapson also worked at commercially undesirable low pH values where the aquo-uranium III ion's existence is possible. Such low pH values in commercial practice would be expected to adversely affect pulp properties.
In "Chelating Agents and Metal Chelates", Dwyer and Mellor, Ed., Academic Press, N.Y. and London (1964) pp. 264 to 267 and 305 to 309 the properties of chromuim and vanduim chelates are discussed. That chromium II and vanadium II are strongly reducing in aqueous solution when complexed with certain organic ligands is disclosed. Suggestion for use other than as general strong reductants in aqueous solution (if the Cr II -EDTA complex were capable of existence) are not suggested.
Neither reference contains anything which would lead one of skill in the art to combine their disclosures so as to be able to predict with any degree of certainty that certain organic ligand complexes of vanadium II, of chromium II, or of titanium II which is not even discussed, would be capable of acting as bleaching reductants for lignin in wood.
Certainly neither reference suggests that these reducing complexes can be continuously regenerated electrochemically and repeatedly recycled to provide an economical, pollution free reductive bleach.
SUMMARY OF THE INVENTION
The invention provides a process comprising treating lignocellulosic pulp in aqueous solution and in a substantially non-oxidizing environment with a polydentate ligand complex of Cr ++ , V ++ or Ti ++ formed by electrochemical reduction of the complexed metal ion.
The tangible embodiments produced by the process aspect of the invention are lignocellulosic pulps of enhanced brightness which are formable or otherwise convertible by standard methods into conventional paper products.
Special mention is made of aspects of the invention wherein the lignocellulosic pulp is mechanical wood pulp, of aspects of the invention wherein the lignocellulosic pulp is chemical wood pulp, of aspects of the invention wherein the polydentate ligand is an aminopolycarboxylic acid such as ethylene diamine tetraacetic acid, 1, 2-diaminocyclohexanetetraacetic acid, or diethylenetriaminopentaacetic acid, of aspects of the invention wherein the polydentate ligand is 8-hydroxyquinoline, or a substituted 8-hydroxyquinoline such as, 8-hydroxyquinoline-5-sulfonic acid. Special mention is also made of aspects of the invention wherein the polydendate ligand complex is recycled through the use of electrochemical reduction to regenerate the reduced form of the complex.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic cross sectional view of an electrochemical cell suitable for practicing the invention.
FIG. 2 is a schematic representation of an electrochemical cell illustrating the principal cell reactions thought to occur during the practice of the invention.
FIG. 3 is a schematic diagram of an alternative apparatus suitable for the practice of the invention.
FIG. 4 is an illustration of the effect of reaction pH on the final brightness of pulp treated in the process of the invention.
FIG. 5 is an illustration of the effect of reaction temperature on the final brightness of pulp treated in the process of the invention.
FIG. 6 is an illustration of the dependency on reaction time of the brightness of pulp treated in the process of the invention at 52° C. and 82° C.
FIG. 7 is an illustration of the relationship between pulp consistency in the reaction and pulp brightness obtained from the process of the invention.
FIG. 8 is an illustration of the relationship between the concentration of chromium-ethylenediamine-tetraacetic acid (EDTA) complex in the reaction and pulp brightness obtained in the process of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, the manner of practicing the process of the invention to produce the brightened lignocellulosic pulps thereof will now be described with reference to a specific embodiment thereof, namely bleaching of ground wood pulp by treating such pulp with an ethylenediamine-tetraacetic acid complex of divalent chromium.
Turning now to FIG. 1, electrochemical cell 1 having walls 2, and bottom 3 is shown in cross section. Contained in electrochemical cell 1 are cathode 4, conveniently a mercury pool cathode, ground wood pulp 5 in suspension in an aqueous solution of an ethylenediamine-tetraacetic acid (EDTA) complex of chromium 6. The pulp 5 is maintained in suspension and the EDTA-chromium solution is stirred conveniently by agitator or stirrer 7. In cell 1, anode compartment 8 surrounding anode 18 is separated from cathode compartment 9 containing cathode 4 by semipermeable membrane 10 and contains an electrolyte solution 11 comprising an aqueous solution of the proton acid 12 of the anion present to balance the positive charge on the chromium EDTA complex. Electrical current 13 to cell 1 is supplied from a current source 14, not shown, through conductors 15 contacting cathode 4 and electrolyte solution 11 though anode 18. It is convenient to exclude air and oxygen from the cathode compartment 9 of cell 1 and the solutions and suspension contained therein by the use of standard techniques, such as, blanketing with an inert gas 16 e.g., nitrogen 16a.
Turning now to FIG. 2 which illustrates schematically the process occurring when the invention is practiced in a cell analogous to the design of cell 1, current 13 supplies electrons 17 to cathode 4 which contacts aqueous solution of EDTA chromium complex 6 represented by the symbol ML having suspended therein pulp 5. As may be seen, oxidized EDTA-chromium complex 6a, that is EDTA-chromium +3, contacts cathode 4 where it is reduced to reduced EDTA-chromium complex 6b, that is EDTA-chromium +2 which contacts pulp 5 reductively reducing its color and itself being reoxidized to 6a.
In anode compartment 8, separated from cathode compartment 9 by semipermeable membrane 10, water is electolyzed at anode 18 liberating electrons 17 carried away from anode 18 as current 13. Also produced at anode 18 are protons 19 and oxygen 20 which may conveniently be vented to the atmosphere. The cell current is carried by migration of protons 19 through semipermeable membrane 10 from anode compartment 8 to cathode compartment 9.
While the apparatus and process illustrated by and described in connection with FIGS. 1 and 2 typify apparatus and processes wherein pulp 5 is bleached by contact with the reduced EDTA-chromium complex 6b in the cathode compartment 9 of cell 1 wherein the EDTA complex 6b is formed, one of skill in the art will recognize that it is also possible to treat pulp 5 with reduced EDTA-chromium complex 6b in a vessel separate from the cathode compartment 9. FIG. 3 is a schematic illustration of an apparatus for doing so.
Referring now to FIG. 3, cell 101, having walls 102 and bottom 103 includes mercury cathode 104 contacting an aqueous solution of an EDTA complex of chromium 106 retained in cathode compartment 109 separated from anode compartment 108 by semipermeable membrane 110. Anode compartment 108 contains electrolyte solution 111, again an aqueous solution of the proton acid 112 of the anion present to balance the positive charge on the EDTA chromium complex 106 in cathode compartment 109. Electrical current 113 is provided to cell 101 by current source 114 and is carried by conductors 115 contacting cathode 104 and anode 118 which in turn contacts electrolyte 111.
The cell reactions in cathode compartment 109 and anode compartment 108 are analogous to those described in connection with and with reference to FIG. 2. As a result of the cell reactions, oxidized EDTA-chromium 106a is converted by contact with cathode 104 to reduced EDTA-chromium 106b in cathode compartment 109 and oxygen 120 is liberated at anode 118 in anode compartment 108.
To bleach pulp 105, the aqueous solution of 106b, reduced EDTA-chromium complex, is transferred through conduit 121 to vessel 122 where sufficient nitrogen gas 116a is introduced through conduit 123 to provide a nitrogen over pressure and exclude air and oxygen throughout the system through which the aqueous solution containing EDTA chromium complex 106 circulates. The solution now containing nitrogen 116a and reduced EDTA-chromium complex 106b is transferred to tower 125 containing ground wood pulp 105. The solution of 106b contacts pulp 105 while passing through the mass of said pulp, reductively bleaching it while at least a portion of 106b is oxidized to EDTA-chromium +3 complex 106a.
The spent solution containing 106a is exhausted from tower 125 and passes through conduit 126 to pump 127, passes through pump 127 and is returned through conduit 128 to cathode compartment 109 where 106a is again reduced to 106b for recycle through the process. Pump 127 supplies the hydrostatic pressure necessary for the circulation of the solution containing the EDTA-chromium complexes 106.
One of skill in the art will recognize that in addition to the ground wood pulp illustrated above, any mechanical or chemical pulp containing chromophores substantially due to the presence of lignin which are convertible to a colorless or a less intensely colored state by reduction may be reductively bleached by the process of the invention. Illustrative of such pulps are refiner mechanical pulp, thermo-mechanical pulp, Asplund pulp, and "unbleached" or chemical pulps partially "bleached" by delignifying "bleaching". In addition, to the wood pulp specifically illustrated hereinabove, one of skill in the art will recognize that other traditional vegetable fibers prepared by the above pulping methods will be suitable for use in the invention. Illustrative of these are fibers from bamboo, bagasse, straw, flax, kenaf, hemp, jute and the like.
One of the skill in the art will also recognize that in addition to the ethylenediamine-tetraacetic acid illustrated above as a polydentate ligand forming the chromium complex exployed as the active reagent in the process of the invention, other polydentate ligands inert under the conditions of the process of the invention may be employed. Such equivalent ligands will be readily apparent to one of skill in the art. Illustrative of such other equivalent ligands are: aminopolycarboxylic acids such as, 1,2-diaminocyclohexane-tetraacetic acid, and diethylenetriaminopentaacetic acid; 8-hydroxyquinoline or substituted 8-hydroxyquinolines such as, 8-hydroxyquinoline-5-sulfonic acid.
In addition to the dipositive chromium complexed with polydentate ligands illustrated above, the invention contemplates as full equivalents polydentate ligand complexes of dipositive vanadium and of dipositive titanuim, prepared and used in analogous fashion to the preparation and use of dipositive chromium complexes.
To Prepare the EDTA-chromium complex or the other metal-liquid complexes contemplated as equivalent by the invention to an appropriate concentration of a desired chromium, vanadium, or titanium salt in water may be added a desired molar equivalent of ethylene diamine tetraacetic acid or a salt thereof or a water soluble form of any of the other polydentate complexing agents contemplated as equivalent by the invention at an elevated temperature and with agitation until conductivity measurements indicate that complexation is complete.
The concentration of the polydentate ligand complex of chromium, vanadium or titanium may vary within wide limits. The concentration may range from minimal to the upper limit of solubility of the complex, preferably from about 0.1 millimole (mM) per liter to about 100 mM per liter, most preferably from about 2.0 mM per liter to about 5.0 mM per liter.
The water soluble salt of chromium, vanadium or titanium employed may be a salt of any convenient anion. For use in a typical paper mill sulfate salts will be preferred for obvious reasons.
The pH range for the practice of the invention may vary widely, preferably within the range of about 2.0 to about 9.0 pH most preferably from about 3.0 to about 4.0 pH.
The temperature and pressure for the practice of the invention may also vary with wide limits. The temperature may range from about room temperature up to 180° C., temperatures from about about 25° C. to about 90° C. when operating at normal atmospheric pressure are preferred. Pressures from about normal atmospheric pressure up to about 200 psi (pounds per square inch) over pressure may be employed.
In addition to the mercury pool cathode illustrated, the invention contemplates other known high hydrogen overvoltage cathodes as full equivalents. Illustrative of these are cathodes fabricated from materials such as, lead, metal amalgams, cadmium, graphite, and zinc. In addition low hydrogen over voltage cathodes such as iron may be employed if suitable conventional hydrogen suppressing additives are added to the cell solution. Typical of such additives are quaternary ammonium salts.
The semi permeable membranes employed to separate the anode and cathode compartments may be any inert semi permeable membrane known in the art. Membranes sold under the Dupont Co tradename Nafion are suitable. The membrane serves to prevent oxygen from reaching and reacting with the reduced complex in the cathode compartment, thereby reducing the efficiency of the desired bleaching reaction. In addition, the membrane serves to prevent the reduced complex from being reoxidized by contact with the anode.
The positive electrode (anode) may preferably be nickel or stainless steel when the pH of the system is alkaline and lead is preferred when the pH of the system is acidic, particularly when the anion employed is sulfate.
One of skill in the art will also recognize that the oxidizing capability of the anode may be employed to produce other oxidants besides oxygen in the anode compartment. Illustrative are such oxidants as perborate, persulfate and perchlorate.
The following examples further illustrate the best mode contemplated by the inventors for the practice of their invention.
EXAMPLE 1
Southern pine groundwood, initial GE brightness 60.8, is stirred at 0.75 consistency in a Na 2 SO 4 -H 2 SO 4 electrolyte solution at pH 4 containing 5.0 millimole (mM) per liter chromium II--EDTA complex for 3 hours at 85° C. The cathode is a mercury pool cathode maintained at about -1.30 volts verus a saturated calomel electrode. The suspension is then cooled, filtered and the pulp collected on the filter throughly washed to remove all traces of the chromium complex. A sheet formed from the pulp and dried by standard techniques had a GE brightness of 81.9% reverting to 70.2% after exposure to steam in the presence of air at 100° C. for one hour followed by drying of the sample at room temperature (23° C.) and then measuring the brightness (reverted brightness).
EXAMPLE 2
Following a proceedure analogous to that described in Example 1 for the reductive bleaching of southern pine groundwood with EDTA-chromium II complex, recycled newsprint, northern pine groundwood (NPGW) and southern pine groundwood (SPGW) are reductively bleached by the catalysts listed in Table 1 at the catalyst concentration, temperature of treatment, and for the times shown in the Table. The initial, final and reverted brightness determined as in Example 1 are also tabulated.
TABLE 1__________________________________________________________________________ Initial Final Reverted Reductive Bl. Agent Bright- Bright- Bright- Bleaching Conc. Duration Temp ness ness nessPulp Type Agent (m.M/1.) (hours) (°C.) (% GE) (% GE) (% GE)__________________________________________________________________________NPGW sodium 3.2 5 60 64.9 75.5 -- hydro- sulfiteNPGW V:EDTA 2.0 5 60 64.9 81.4 74.4 (1:2)SPGW V:DACTA 5.0 24 25 60.8 74.9 -- (1:1)SPGW V:OXINE 5.0 17 25 60.8 71.6 64.0 (1:3)SPGW V:DACTA 5.0 2 86 60.8 66.7 (1:1)Recycled Cr:DTPA 5.0 3 85 56.0 72.3 65.9Newsprint (1:1)__________________________________________________________________________ Notes: 1. Newsprint was deinked by standard methods employed in the industry 2. DACTA is 1,2diaminocyclohexanetetraacetic acid 3. OXINE is 8hydroxyquinoline-5-sulfonic acid 4. DTPA is Diethylenetriaminopentaacetic acid
EXAMPLE 3
Employing conditions analogous to those of Example 1, samples of northern pine groundwood, initial brightness 64.2% GE, are treated at varying electrolyte pH values at 52° C. for three hours with chromium II--EDTA complex. The final brightness values obtained are shown in FIG. 4.
EXAMPLE 4
Employing conditions analogous to those of Example 1, samples of northern pine groundwood, initial brightness 64.2% GE, are treated at varying temperatures for three hours with chromium II--EDTA complex. The final brightness values obtained are shown in FIG. 5.
EXAMPLE 5
Employing conditions analogous to those of Example 1, sample of northern pine groundwood, initial brightness 64.2% GE, are treated at 82° C. (curve with greater slope) or 52° C. (curve with lesser slope) with chromium II--EDTA complex for varying periods of time. The final brightness values found are shown in FIG. 6.
EXAMPLE 6
employing conditions analogous to those of Example 1, samples of northern pine groundwood, initial brightness 64.2% GE, are treated at 52° C. at varying consistencies with chromium II--EDTA complex. The final brightness values found are shown in FIG. 7.
EXAMPLE 7
Employing conditions analogous to those of Example 1, samples of northern pine groundwood, initial brightness 64.2% GE, are treated at 52° C. with varying concentrations of chromium II--EDTA complex, conveniently measured by varying the initial concentration of chromium III--EDTA complex initially introduced into the reaction. The final brightness values found are shown in FIG. 8.
The subject matter which applicants regard as their invention is particularly pointed out and distinctly claimed as follows:
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Reductive bleaching of lignin containing pulps employing polydentate ligand complexes of dipositive vanadium, chromium and titanium. High brightness pulps with good reversion stability are obtained. The process is essentially polution free as the reduced complexes can be repeatedly regenerated electrochemically.
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FIELD OF THE INVENTION
[0001] The present invention relates generally to integrated circuits, and more particularly to integrated circuit packages and packaging techniques.
BACKGROUND OF THE INVENTION
[0002] With the continued anticipation of higher speed requirements in the computer hard drive industry, a transition from Parallel Advanced Technology Attachment (PATA) interfaces to Serial Advanced Technology Attachment (SATA) interfaces is currently underway. See, e.g., J. Donovan, “Here Comes Serial ATA,” E. E. Times, April 2003; and L. Wood, “SATA: Evolutionary or Revolutionary Disk Technology,” EnterpriseStorageForum.com, March 2003. SATA meets the rising hard drive performance requirements without significant increases in price. Further, SATA improves airflow and cuts power consumption by replacing PATA ribbon cables with low voltage serial cables. A SATA interface is typically integrated in a System-on-Chip (SOC) configuration. Such SOCs are frequently utilized in desktop computers. Due to extreme cost pressure in the industry, package solutions for SOCs that offer the right level of performance, while having the lowest cost, will be sought for use in the higher speed systems. Thus, the increased performance demands of the systems have not stopped production and use of traditional leadframe-based packaging. Recent innovations have allowed the more traditional package structures to reach into the markets of the more demanding applications. See, e.g., S. Jewler, “Current Challenges Dictated by Today's IC Packaging Trends,” Solid State Technology, April 2003.
[0003] A standard SOC is a Thin Quad Flat Package (TQFP) which provides a space efficient packaging solution, resulting in smaller PWB space requirements. The TQFP includes a central die upon which an integrated circuit device is disposed. The central die is electrically connected to a plurality of leads that extend outward from the die and beyond the packaging, or the material which encapsulates the die and the leads. The ends of the leads may then be soldered to traces on a PWB. The reduced height and body dimensions of the TQFP are ideal for space-constrained applications, such as laptop PCs, video/audio devices, data acquisition devices, office equipment, disc drives, and communication boards.
[0004] A preferred SOC package is the Exposed Pad Thin Quad Flat Package (ETQFP). A more particular example of such a package is the ExposedPad L/TQFP commercially available from Amkor Technology of West Chester, Pa., U.S.A. In this type of package, the integrated circuit die is shifted downward and an associated die pad is exposed on the underside of the package. The exposed die pad significantly increases the thermal efficiency of the package. The ETQFP can increase heat dissipation by as much as 110% over a standard TQFP, thereby expanding operating parameter margins. Additionally, the exposed pad can be connected to ground, thereby reducing loop inductance for high-frequency applications. The exposed pad is soldered directly to the PWB to realize the thermal and electrical benefits.
[0005] An additional product also available from Amkor Technology is the MicroLeadFrame, which replaces all the traditional leadframe leads on the perimeter of the integrated circuit package with lands on an underside of the package. The lands are used to provide electrical connection of the integrated circuit package to the PWB. This modification allows package size to be reduced, while also reducing lead inductance for high-frequency applications. This technology also incorporates the exposed pad on the bottom surface of the package to provide an efficient heat path.
[0006] The adaptation of these packages is intended to extend the useful life of the low-cost TQFP, so that it may comply with anticipated higher speed requirements of the systems, while remaining inexpensive. However, a problem exists in that users generally prefer a circuit board arrangement having high-speed lines that may be routed to an integrated circuit on a top surface of a PWB, while maintaining the traditional properties of TQFPs, such as leadframe leads. Conventional TQFPs, including the above-noted ETQFP, typically do not include high-speed leads, and instead have leadframe leads with a tight pitch preventing trace access to the underside of the packaged integrated circuit from the top surface of the PWB. The MicroLeadFrame is smaller in size than traditional TQFPs and does not provide leadframe leads. Thus, a need exists for an improved package that addresses the drawbacks of the conventional arrangements.
SUMMARY OF THE INVENTION
[0007] The present invention in accordance with one aspect thereof provides a packaged integrated circuit that allows for the routing of high-speed signals out from high-speed leads on an underside of the packaged integrated circuit, across the top surface of a PWB or other type of circuit mounting structure, to a high-speed connector on the circuit mounting structure.
[0008] For example, one aspect of the invention is a packaged integrated circuit comprising a die. A package body is formed from encapsulant and at least partially encloses the die. A leadframe is also connected to the die and partially enclosed in the package body. Leads extend out from the package body and a subset of these leads are separated by a lead-to-lead pitch. At least two adjacent leads of the leadframe are separated by a space larger than the pitch. An additional lead, not part of the lead frame, is also connected to the die and disposed on an underside of the package. The additional lead is connectable to a PWB trace or other circuit mounting structure trace passing between the adjacent leads separated by the space larger than the pitch.
[0009] The present invention may further comprise a PWB, or other type of circuit mounting structure, having at least one electrical connector, a plurality of traces, and at least one packaged integrated circuit, as described above, mounted thereon. At least one trace is routed on the top surface of the circuit mounting structure, from the electrical connector, passing between the adjacent leads separated by the space larger than pitch, to an additional lead on the underside of the packaged integrated circuit.
[0010] The present invention may also comprise a leadframe for use in a packaged integrated circuit having a plurality of leads. At least two adjacent leads of the leadframe are separated by a space larger than the pitch, so that when the leadframe is used in a packaged integrated circuit, a trace on a circuit mounting structure is connectable to an additional lead on an underside of the package body.
[0011] Advantageously, the packaged integrated circuit allows high-speed traces to be routed on a top surface of a circuit mounting structure, through the space that is larger than the pitch, to the exposed surface of the additional lead. Additionally, such an arrangement may extend the useful life of a low-cost package solution by allowing it to be incorporated into systems that have higher speed requirements.
[0012] These and other objects, features, and advantages of the present invention will become apparent from the following detailed description of illustrative embodiments thereof, which is to be read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a diagram illustrating a bottom view of a packaged integrated circuit, according to an embodiment of the present invention;
[0014] FIG. 2A is a diagram illustrating a partial view of a leadframe for an integrated circuit, according to an embodiment of the present invention;
[0015] FIG. 2B is a diagram illustrating a magnified view of the leadframe of FIG. 2A showing a locking mechanism, according to an embodiment of the present invention; and
[0016] FIG. 3 is a diagram illustrating a top view of a PWB having a packaged integrated circuit mounted thereon, according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] As will be illustrated in detail below, the present invention in an illustrative embodiment provides a packaged integrated circuit that allows for the routing of high-speed signals out from high-speed leads on an underside of the packaged integrated circuit. The high-speed signals may then be routed across a top surface of a PWB, or other type of circuit mounting structure, to a high-speed connector.
[0018] Referring initially to FIG. 1 , a diagram illustrates a bottom view of a packaged integrated circuit 100 , according to an embodiment of the present invention.
[0019] Packaged integrated circuit 100 is suitable for mounting on a PWB or other type of circuit mounting structure. It will be assumed for the remaining description that the circuit mounting structure in the illustrative embodiment is a PWB.
[0020] At the center of packaged integrated circuit 100 is a die 102 . Die 102 generally includes at least one integrated circuit device. Packaged integrated circuit 100 comprises a package body 104 , formed from encapsulant. Die 102 is substantially surrounded by package body 104 , but a portion of its bottom surface is exposed through the bottom surface of package body 104 . Additional leads 106 are also substantially surrounded by package body 104 , with portions of additional leads 106 exposed through the bottom surface of package body 104 . Additional leads 106 are electrically connected to the integrated circuit device within package body 104 . Die 102 significantly increases the thermal efficiency of packaged integrated circuit 100 and may be connected to ground, reducing loop inductance for high-frequency applications. In such a case, die 102 is soldered directly to a PWB, to realize the thermal and electrical benefits. While the present embodiment shows die 102 exposed on the bottom surface for thermal purposes, it is also possible to have a packaged integrated circuit without an exposed die 102 . In such a case die 102 would be completely surrounded by package body 104 and would not be visible when viewing packaged integrated circuit 100 .
[0021] Additional leads 106 are preferably disposed on an underside of packaged integrated circuit 100 a short distance from die 102 so that they have the shortest trace length from the integrated circuit device. Additional leads 106 are connected to die 102 in a conventional manner, preferably through wire bonding. The shorter the trace length, the lower the lead inductance, and the higher the speed that may be achieved at additional leads 106 . In the present embodiment, four additional leads 106 are disposed on a single side of die 102 . However, any number of additional leads 106 may be disposed on any or all of the sides of die 102 . Further, while it is preferable for additional leads 106 to be disposed adjacent to die 102 , they may be disposed anywhere on the underside of packaged integrated circuit 100 . However, the shortest distance from die 102 is most preferable due to the reasons specified above.
[0022] In the illustrative embodiment of FIG. 1 , leadframe leads 108 run through and project out from package body 104 along the perimeter of packaged integrated circuit 100 . This is similar to a traditional TQFP arrangement. However, the invention can be implemented using a wide variety of other packaging arrangements. Leadframe leads 108 are formed and shaped from a leadframe, an example of which is shown in FIG. 2A . Leadframe leads 108 are also electrically connected to the integrated circuit device mounted on die 102 within package body 104 . This electrical connection is preferably implemented using a wire bonding technique.
[0023] The spacing between leadframe leads 108 at the perimeter of packaged integrated circuit 100 is defined as the pitch. For example, the pitch of leadframe leads 108 in the illustrative embodiment may be approximately 0.4 mm to 0.5 mm. Other lead pitches may be used in alternative embodiments. Leadframe leads 108 in the illustrative embodiment are, by way of example, approximately 0.13 to 0.27 mm in width. Also, in accordance with the invention, a large pitch 110 exists between a pair of adjacent leadframe leads 108 . The width of large pitch 110 may be determined by adding a combination of lead widths and pitches. When packaged integrated circuit 100 is mounted on a PWB, large pitch 110 permits high-speed lines to be routed between this pair of adjacent leadframe leads 108 , providing access to additional leads 106 on an underside of packaged integrated circuit 100 .
[0024] In the present embodiment a single large pitch 110 is shown. However, multiple large pitches 110 may exist along the perimeter of packaged integrated circuit 100 . The number and placement of large pitches 110 along the perimeter of packaged integrated circuit 100 may correspond to the number and placement of additional leads 106 surrounding die 102 on the underside of package body 104 .
[0025] Large pitch 110 is preferably disposed at the nearest point along the perimeter of packaged integrated circuit 100 from additional leads 106 . Thus, large pitch 110 may be disposed along any side of packaged integrated circuit 100 .
[0026] Referring now to FIG. 2A , a diagram illustrates a partial view of a leadframe 200 for a packaged integrated circuit 100 , according to an embodiment of the present invention. Leadframe 200 shows leadframe leads 208 before they are trimmed and formed, before connection to die 102 , and before encapsulating material is applied. A locking mechanism 212 is disposed at a specific point along the perimeter of leadframe 200 , and in place of at least one leadframe lead 208 . Locking mechanism 212 , in the illustrative embodiment, creates a large pitch between two neighboring leadframe leads 208 . Large pitch 210 is greater than the pitch between the remaining pairs of leadframe leads 208 . The width of large pitch 210 is determined by the number of leadframe leads 208 locking mechanism 212 replaces. The present embodiment shows locking mechanism 212 replacing two leadframe leads 208 . Therefore, the width of large pitch 210 may be determined by the equation:
LP=wx+p ( x+ 1)
where LP represents the large pitch, w represents the width of leadframe leads 208 , p represents the pitch between leadframe leads 208 , and x represents the number of leadframe leads 208 replaced by locking mechanism 212 .
[0028] Referring now to FIG. 2B , a diagram illustrates a magnified view of leadframe 200 of FIG. 2A showing locking mechanism 212 , according to an embodiment of the present invention. Locking mechanism 212 is connected to leadframe 200 and leadframe leads 208 A and 208 B by dambar 214 . Dambar 214 represents the individual sections of leadframe between leadframe leads 208 and locking mechanism 212 . Locking mechanism 212 and dambar 214 keep leadframe 200 stable during manufacturing in place of the depopulated leadframe leads replaced by locking mechanism 212 . Therefore, the manufacturing process of leadframe 200 does not require existing manufacturing equipment to be changed.
[0029] During manufacturing, after leadframe 200 is wire-bonded to the die, encapsulant material is formed over leadframe 200 to form package body 104 . Dambar 214 is a portion of leadframe 200 that prevents encapsulating material from flowing to the ends of leadframe 200 , thus forming perimeter 216 of package body 104 and permitting portions of leadframe leads 208 to remain exposed. Locking mechanism 212 is partially covered by the encapsulating material leaving only a small extension of its legs exposed beyond perimeter 216 . This small exposure of the legs of locking mechanism 212 is not shown, but each exposed leg represents where a leadframe lead would normally protrude from package body 104 . Leadframe leads 208 are then trimmed and formed and portions of dambar 214 between each leadframe lead 208 and leg of locking mechanism 212 are punched out. The horseshoe shape of locking mechanism 212 prevents it from being pulled out during the trimming and forming of leadframe leads 208 and the removal of dambar 214 . If locking mechanism 212 were to be pulled out it would result in holes in package body 104 on a perimeter 216 of the packaged integrated circuit.
[0030] Locking mechanism 212 may take other shapes. For example, in accordance with the current embodiment, if locking mechanism 212 were to replace an additional leadframe lead 208 , locking mechanism 212 would comprise three prongs, forming an M-shape. While the present embodiment shows locking mechanism 212 having a shape with prongs, different forms are also possible that achieve the same result.
[0031] Referring now to FIG. 3 , a diagram illustrates a top view of a PWB 318 having mounted thereon a packaged integrated circuit 300 , according to an embodiment of the present invention. Leadframe leads 308 of packaged integrated circuit 300 are soldered to corresponding traces 320 on PWB 318 . Traces 320 are routed on a top surface of PWB 318 from a connector 324 to leadframe leads 308 . High-speed traces 322 may be routed on the top surface of PWB 318 from connector 324 through a large pitch, beneath packaged integrated circuit 300 , to additional leads 306 on an underside of packaged integrated circuit 300 . Critical signals may be routed through high-speed traces 322 on the top surface of PWB 318 , while less critical signals may be routed through leadframe leads 308 or in lower layers of PWB 318 . For example, lower-speed data and control signals may be carried by leadframe leads 308 and traces 320 , while additional leads 306 and high-speed traces 322 may carry higher-speed signals, such as signals having a frequency of at least 2 GHz.
[0032] Packaged integrated circuit 300 may be disposed anywhere on PWB 318 . The present embodiment shows a single packaged integrated circuit 300 on PWB 318 , however a plurality of packaged integrated circuits 300 may be disposed thereon. Further, the present invention shows a single connector 324 on PWB 318 , however, a plurality of connectors 324 may be disposed thereon. Connectors 324 may also be disposed in a multitude of positions on PWB 318 . The present embodiment shows traces 320 and 322 taking specific paths from connectors 324 to packaged integrated circuit 300 , however, traces 320 and 322 can take any path on PWB 318 to reach their destination. Traces 320 and 322 are shown to be routed on a top surface of PWB 318 , which is preferred for high-speed traces 322 . However, traces 320 and 322 may also be routed on a different layer of PWB 318 . FIG. 3 shows packaged integrated circuit 300 having a plurality of additional leads 306 and leadframe leads 308 . As described above, additional leads 306 and leadframe leads 308 may vary in number and placement in packaged integrated circuit 300 . Finally, FIG. 3 shows an embodiment of the present invention on a PWB, however, it is also possible to mount the present invention on other circuit mounting structures.
[0033] Accordingly, as described herein, the present invention in the illustrative embodiment provides a high-speed packaged integrated circuit for installation on a PWB or other type of circuit mounting structure. More particularly, the present invention provides an improved packaged integrated circuit that allows for routing of high-speed traces on the top surface of the PWB from high-speed leads to a high-speed connector.
[0034] Although illustrative embodiments of the present invention have been described herein with reference to the accompanying drawings, it is to be understood that the invention is not limited to those precise embodiments, and that various other changes and modification may be made by one skilled in the art without departing from the scope or spirit of the invention.
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A packaged integrated circuit for installation on a printed wiring board (PWB) or other type of circuit mounting structure, that allows for the routing of high-speed signals out from high-speed leads on an underside of the packaged integrated circuit. The packaged integrated circuit comprises a die and a package body formed from encapsulant that at least partially encloses the die. A leadframe is also connected to the die and partially enclosed in the package body. Leads extend out from the package body and a subset of these leads are separated by a lead-to-lead pitch. At least two adjacent leads of the leadframe are separated by a space larger than the pitch. An additional lead is also connected to the die and disposed on an underside of the package. The additional lead is connectable to a circuit mounting structure trace passing between the adjacent leads separated by the space larger than the pitch.
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CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
This patent application is a continuation of U.S. patent application Ser. No. 11/303,065, entitled “Method and System for Treating Radioactive Waste Water,” filed on 14 Dec. 2005, and published as U.S. Patent Application Publication No. 2007/0131621, which is incorporated by reference herein in its entirety.
TECHNICAL FIELD
The method and apparatus of the invention relate to processing waste water from nuclear power reactors and other sources of water contaminated with radionuclides. In particular, the present method and apparatus are related to processing waste waters contaminated with colloidal, suspended and dissolved radionuclides.
BACKGROUND
In the commercial nuclear power industry, there are primarily two types of reactor systems, namely boiling water reactors (BWR) and pressurized water reactors (PWRs). Both use water to moderate the speed of neutrons released by the fissioning of fissionable nuclei, and to carry away heat generated by the fissioning process. Water flows through the reactor core, is recycled, and inevitably becomes contaminated with iron, Fe-55, colloidal and soluble cobalt, Co-58, and Co-60, and other radionuclides. The water further becomes contaminated with organics (e.g., oils and greases), biologicals and non-radioactive colloids (e.g., iron rust).
In a boiling water reactor (BWR), the water passing through the core will be used directly as steam in driving turbine-generators for the production of electricity. In a pressurized water reactor (PWR), the primary water that flows through the reactor is isolated from the secondary water that flows through the turbine generators by steam generators . In both cases, while the chemical constituents of the waste water will be different, these reactor systems will produce colloidal, suspended and dissolved solids that must be removed before the waste water may be reused or released to the environment.
The presence of iron (as iron oxide from carbon steel piping) in Boiling Water Reactor (BWR) circuits and waste waters is a decades old problem. The presence and buildup of this iron in condensate phase separators (CPS) further confounds the problem when the CPS tank is decanted back to the plant. Iron carryover here is unavoidable without further treatment steps. The form of iron in these tanks, which partially settles and may be pumped to a de-waterable high integrity container (HIC), is particularly difficult and time consuming to dewater. The addition of chemicals upstream from the CPS, such as flocculation polymers, to precipitate out the iron only produces an iron form even more difficult to filter and dewater. Such chemically pretreated material contains both sub-micron particles and floc particles of sizes up to 100 microns. It is believed that the sub-micron particles penetrate into filter media, thus plugging the pores and preventing successful filtration of the larger micron particles.
Like BWR iron waste waters, fuel pools, or basins, (especially during the decontamination phase) often contain colloids which make clarity and good visibility nearly impossible. Likewise, miscellaneous, often high conductivity, waste steams at various plants contain such colloids as iron, salts (sometimes via seawater intrusion), dirt/clay, surfactants, waxes, chelants, biologicals, oils and the like. Such waste streams are not ideally suited for standard dead-end cartridge filtration or cross-flow filtration via ultrafiltration media (UF) and/or reverse osmosis (RO), even if followed by demineralizers. Filter and bed plugging are almost assured.
There are a number of prior art techniques used for removal of colloidal, suspended and dissolved solids, and the requirement to remove such materials from waste waters is not unique to nuclear reactors. However, the nature of nuclear reactors raises special concerns about the use of additives for chemical treatments because of the desire to avoid making radioactive wastes also chemical wastes.
There are other concerns as well. The processed waste water must be quite free of radioactive contaminants if it is to be released to the environment. The radioactive material extracted from the waste water during processing must be stable or in a form that can be stabilized for disposal in a way that meets disposal site requirements, particularly with respect to preventing the leaching out of radioactive contaminates by liquid water. Finally, the volume of the waste must be minimized because of both the limited space available for disposal of radioactive waste and the high cost of its disposal.
Accordingly there is a need for better ways of processing radioactive waste water containing suspended solids and dissolved ions from nuclear power reactors and other sources.
SUMMARY
The key to solving the above dilemmas is 1) to break the colloid by neutralizing the outer radius repulsive charges of similar charged colloidal particles, and 2) to cause these neutralized particles to flocculate and form a type of flocculent (floc) that is more readily filterable, and thus de-waterable. In the present invention, these tasks are carried out with the innovative application of an electro-coagulation (EC) unit to electrolytically seed the waste feed stream with a metal of choice, and without prior addition of chemicals common to ferri-floccing or flocculation/coagulation polymer addition. Once the colloid has been broken and floccing has begun, removal of the resultant floc can be carried out by standard backwashable filters, cross-flow filters (e.g., UF), or, in simple cases, dead-end filters. Such applications include low level radioactive waste (LLW) from both PWRs and BWRs, fuel pools, storage basins, salt water collection tanks and the like.
For the removal of magnetic materials, such as some BWR suspended irons (e.g., boiler condensates and magnetite and hemagnetite), an electromagnetic filter (EMF) unit may be coupled with the EC unit. For the removal of non-magnetic materials, the EC treatment may be followed by treatment with a flocculating chemical, such as a flocculating polymer like Betz-1138 which is a polyacrylamide copolymer available from the Betz Corporation. For a waste stream containing magnetic materials and one or more non-magnetic species, e.g., cesium (Cs), a magnetic seeding step for coupling the non-magnetic species to a magnetic moiety, e.g., CHFC (Cobalt hexaferricyanate), to form a magnetic chemical complex may be followed by the EMF for the effective removal of this complex.
Thus, the invention provides a method, apparatus and system for removing contaminants from radioactive waste waters by using electro-coagulation in combination preferably with magnetic filtration and/or treatment with a flocculation agent. The electro-coagulation may also be used to enhance the subsequent removal of contaminants by dead end filtration, high gradient magnetic filtration (HGMF), ultra-filtration (UF), back flushable filters (BFF), and high integrity containers (HICs) that are dewaterable with sheet filters. The electro-coagulation takes place after adjustments of the pH and the conductivity of the waste water, if needed. Sacrificial metal electrodes, which may be iron but preferably are aluminum, are used in batch or continuous electrolytic processing of the waste water to seed it with positively charged metal ions that neutralize and agglomerate negatively charged ions, suspended particles and colloidal particles.
The electro-coagulation (EC) process of the invention works on an electricity-based technology that passes an electric current through radioactive waste waters. Thus, electro-coagulation utilizes electrical direct current (DC) to provide cations from the sacrificial metal electrode ions (e.g., Fe or Al) that agglomerate and thereby precipitate out undesirable contaminates, including dissolved metals and non-metals, e.g., antimony (Sb). The electrical DC current is preferably introduced into the aqueous feed stream via parallel plates constructed of the sacrificial metal of choice. This process avoids the use of undesirable chemical additions (e.g., ferric chloride).
Moreover, the anode and cathode will hydrolyze water molecules, liberating oxygen and hydrogen, respectively, as tiny bubbles, the latter combining with many of the dissolved ions in the water to form insoluble oxides. The oxygen and hydrogen also will cause small, light particles to float and flocculate (e.g., oils and greases) so that they can also be skimmed off or filtered out. Some of these lighter particles are biological particles such as bacteria that have been destroyed by electro-osmotic shock.
The use of electro-coagulation with radionuclides has several specific advantages in addition to the fact that it will cause the precipitation or flotation of radionuclide species in the waste water. One of these is the oxidation of some species to render them stable in water. The oxidized species are then not toxic hazards and are not likely to be leached into the ground water if buried. They will generally pass the EPA TCLP test, which will result in significant cost savings in disposal. The production of oxygen through hydrolysis also acts as a bactericide and fungicide to further remove wastes other than purely radioactive wastes.
In addition to radionuclides, the waste waters may be contaminated by one or more of heavy metals, colloids, clay, dirt, surfactants, cleaners, oils, greases, biologicals, and the like. As these contaminated waste waters are passed through one or more EC cells, the following four treatment reactions occur:
1. Coagulation—Ions, colloids and suspended solids will remain suspended indefinitely in solution due to their like charges, which are usually negative. Thus, they repel each other and do not allow coagulation or floccing. As contaminated water passes through the cell assembly, DC power is applied continuously, or is pulsed, to the cell electrodes. Metallic ions from the positive cell electrodes (anodes) slough off and provide bridging seeds to the suspended solids and other contaminates present. Only as much electrode seed material is supplied as there are dissolved, colloidal and/or suspended solids present, thus controlling the solids addition. The metallic seed ions cause the charge of suspended or dissolved solids, colloids, oils and greases, and the like, to be neutralized. This charge neutralization causes the contaminants to coagulate, or floc, so that they become large enough to settle or float or be filtered by standard filtration media, ultra-filtration (UF), or reverse osmosis (RO), or, if magnetic, by electro-magnetic filtration (EMF) or High Gradient Magnetic Separation (HGMS) filtration. This coagulation process does not require the addition of chemicals with the exception of those for adjusting the pH or conductivity, if required. 2. Oxidation—As waste water contaminated by heavy and/or radioactive metals is passed through the EC cell(s), the metals are reduced to an oxide. The metal ions are thereby changed from a dissolved state to a suspended state and then are precipitated from the water. Heavy metals that are thus oxidized by passing through the electric current will generally pass a TCLP test, which provides significant savings in the cost of sludge disposal. 3. Aeration—A natural byproduct of this EC process is aeration. No air or any other gases need to be injected into the process, as the dissociation products of water form tiny bubbles giving the coagulated contaminants buoyancy. Thus, after treatment of the waste water, oils and greases therein can either be skimmed off, or re-mixed and settled or filtered with the rest of the coagulated sludge. 4. Biologicals—A further advantage of this EC Process is that it is a natural biocidal process because it ruptures microorganisms and the like by electro-osmotic shock.
The magnetic filter may comprise a ferromagnetic filtering medium that is temporarily magnetized when an electro-magnetic field is passed through it via a surrounding coiled electrical conductor. The medium (or media) may comprise steel sheets, screens, beads or balls, the latter being preferred. Upon de-energizing the electro-magnetic field, this filtering medium, which is preferably made of soft magnetic material (e.g. 430 stainless steel), is no longer magnetized to allow the filter to be back-flushed for removal of the coagulated contaminates by flushing them off the filtering media. Thus, the core of the magnetic filter preferably is not made of a permanently magnetizable material but of a soft magnetic material that is electro-magnetizable and then can be demagnetized by simply removing the magnetizing electrical current from the surrounding coil so that the filtering media, preferably 400 series (e.g. 430 S.S.) stainless steel balls, can be backflushed for reuse. The agglomerated particles from the EC unit can also be removed from the waster water by conventional filtration techniques. Furthermore, many of the agglomerated particles may quickly settle out and these may be removed by simply decanting the clarified water. However, the use of an EMF for removal of radioactive precipitates is particularly advantageous because once removed, these waste solids may be easily backflushed to and handled by conventional radioactive waste (radwaste) disposal systems, thereby avoiding the radioactive filter waste generated by mechanical filtering equipment. As used in this specification and the appended claims, the term electromagnetic filtration (EMF) includes high gradient magnetic filtration and other magnetic filtration techniques that magnetically remove ferromagnetic particles or precipitates and that permit the filtered out material to be backflushed to a radwaste system.
Another particular feature of the present invention is that radionuclides which are not ferromagnetic, such as cesium-137, can be removed by the addition of a magnetic complexing agent, such as cobalt hexaferricyanate, which forms a magnetic complex with the radionuclides that can be removed by a magnetic filter.
Some of the advantages of the invention over conventional processes for chemical coagulation and mechanical filtration include the following:
(1) Less Waste Volume is created because there is no need for post ion exchange coupled with UF or the like. (2) Provides consistent introduction of the seeding agent and only as needed, such as Fe or Al, at high throughputs. (3) Provides improved water quality for those radioisotopes that cannot be taken out by UF or standard filtration. (4) Provides operational advantages because there is no chemical introduction, no chloride introduction, and no significant pH swings. (5) Less waste volume is created as compared to using chemical coagulants such as alum or lime, and to using flocculation polymers alone. (6) The coagulant is significantly easier to dewater than chemical and purely polymer sludges because the electrocoagulated floe tends to contain less bound water, is more shear resistant, and is thus more readily filterable. (7) The EC process is capable of acting as a biocide for the destruction of biological organisms because electron flooding of the waste water eliminates the polar effect of water complexes allowing colloidal materials to precipitate, and the increase of electrons creates an osmotic pressure that ruptures bacteria, cysts, and viruses. (8) Metal oxides are formed that will pass TCLP disposal requirements. (9) The EC process is not adversely effected by oils and greases and these contaminates are removed so that the output may be sent to deadend filtration, BFF, EMF, UF or RO. (10) The EC process may be utilized without the introduction of chemicals, including polymers. (11) The process equipment has an extremely small foot print. (12) EC requires simple equipment and is easy to operate with sufficient operational latitude to handle most problems encountered on running. (13) Wastewater treated by EC gives clear, colorless and odorless water. (14) Sludge formed by EC tends to be readily settable and easy to de-water, because it is composed of mainly metallic oxides/hydroxides. Above all, it is a low sludge producing technique. (15) Flocs formed by EC are similar to chemical floc, except that EC floc tends to be much larger, contains less bound water, is acid-resistant and more stable, and therefore, can be separated faster by filtration. (16) EC produces effluent with less total dissolved solids (TDS) content as compared with chemical treatments. If this water is reused, the low TDS level contributes to a lower water recovery cost. (17) The EC process has the advantage of removing the smallest colloidal particles, because the applied electric field readily neutralizes them, thereby facilitating the coagulation. (18) The EC process avoids uses of chemicals and so there is no problem of neutralizing excess chemicals and no possibility of secondary pollution caused by chemical substances added at high concentration as when chemical coagulation of wastewater is used (19) The gas bubbles produced during electrolysis can carry certain pollutants to the top of the solution where it can be more easily concentrated, collected and removed (e.g., by skimming). (20) The electrolytic processes in the EC cell are controlled electrically and with no moving parts, thus requiring less maintenance. (21) The EC technique can be conveniently used in rural areas where electricity is not available since a solar paned attached to the unit may be sufficient to carry out the process.
The sacrificial electrodes are expended by being dissolved into the wastewater stream and eventually need to be replaced. The regularity here depends on the wastewater composition and the volume treated. For nuclear applications, replaceable canisters containing the electrodes would be used. An impermeable oxide film may be formed on the cathode leading to loss of efficiency of the EC unit. However, this does not occur if the unit for the process water is forced into turbulence and this oxide is never allowed to form. Self cleaning by periodic current application, controlled by the computer, will also prevent scaling.
Reasonable levels of conductivity of the wastewater suspension is required. This can be compensated for in low conductivity applications by increasing the electrode area, increasing the residence time (e.g., recycle or additional cells in series), increasing the amperage (e.g., jumpering electrodes to place them in parallel), and/or adding innocuous chemicals to increase conductivity and/or pH (e.g., sodium sulfate or sodium bicarbonate or baking soda).
DRAWINGS
The invention, including its operational steps and the components and systems for carrying out those steps, may be further understood by reference to the detailed description below taken in conjunction with the accompanying drawings in which:
FIG. 1 is a diagrammatic illustration of the system of the invention for carrying out its processing of radioactive waster water;
FIG. 2 illustrates the electro-coagulation unit of the invention;
FIG. 3 illustrates the electromagnetic filtering unit of the invention;
FIG. 4 is an exploded view illustrating details of a modified housing and filtering media for the electromagnetic filtering unit of FIG. 3 ;
FIG. 5 is an enlarged view of a portion of the ferro-magnetic filtering media identified by the circle 5 in FIG. 4 ;
FIG. 6 is an exploded view similar to FIG. 4 showing an alternative embodiment of the ferro-magnetic filtering media;
FIG. 7 is an exploded view similar to FIG. 4 showing a farther alternative embodiment of the ferro-magnetic filtering media; and,
FIG. 8 is an exploded view similar to FIG. 4 showing another alternative embodiment of the ferro-magnetic filtering media.
DETAILED DESCRIPTION
In the electrocoagalation (EC) unit of the invention, a direct current is applied to a cathode-anode system in order to destabilize any dissolved ionic or electrostatically suspended contaminants. During this electrolytic process, cationic species from the metal of sacrificial anodes dissolve into the water. These positively charged cations neutralize and thereby destabilize negatively charged contaminants and also create metal oxides and hydroxides which precipitate and bring down the neutralized contaminants as part of the precipitate. If aluminum anodes are used, aluminum oxides and hydroxides are formed. If iron anodes are used, iron oxides and hydroxides form. Aluminum anodes are preferred for the present invention because iron anodes become readily coated with iron oxide, which interferes with the electrolytic process.
The formation of the metal oxides and hydroxides, and their subsequent precipitation, are similar to the processes which occur during coagulation or flocculation using alum or other chemical coagulants. The difference is that in electrocoagulation, the cations are produced by electrolytic dissolution of the anode metal instead of by adding a chemical coagulant. In addition, the activation energy provided by the application of an electrical current will promote the formation of oxides, instead of hydroxides which may be in a slimy form that may clog filters, if the electrical energy supplied by the unit exceeds the activation energy for formation of the metal oxide. The metal oxides are more stable than the hydroxides and therefore more resistant to breakdown by acids. The dissolved contaminants are incorporated into the molecular structure of these acid resistant precipitates by ion bridging and/or adsorption. Also, the weak intermolecular force known as van der Waalls' force causes these molecules to be attracted to one another and thereby coagulated into a floe. The precipitated floe is often capable of passing the requirements of the TCLP (the EPA's Toxicity Characteristic Leaking Procedure), which will significantly reduce solid waste disposal costs.
In addition, during the electrolytic process, oxygen gas is produced at the anode by the electrolysis of the water molecules. Simultaneous reactions take place at the cathode producing hydrogen gas from the water molecules. These gases can cause the coagulated floe molecules to float, and can also cause flotation and coagulation of oils, greases, and biological materials, such as the residue produced by the rupturing of bacteria and other microorganisms by electro-osmotic shock. The floating floe can be skimmed off for disposal, or it may be subjected to shaking or other turbulence to degas the floc and cause it to settle with the metal precipitates. The coagulation process preferably increases the size of submicron particles to particles as large as 100 microns, preferably to an average size of at least 20 microns so that the precipitate particles are easily removable by a standard 20 or 25 micron filter.
Another important cathodic reaction involves the reduction of dissolved metal cations to the elemental state so that they plate out as a metal coating on the cathodes. Since at least some of these metals will be radioactive, the cathodes of the invention must be regenerated in place by reversing their polarity so that the process anodes become regenerating cathodes and the process cathodes become regenerating anodes to thereby unplate the metal coating from the process cathodes, and by providing a fluid flow past the regenerating anodes (i.e., the process cathodes) to carry off the unplated metal cations to a conventional radioactive waste disposal system.
Referring now to FIG. 1 , there is shown a radioactive water treatment system, generally designated 10 , wherein the pH and the conductivity of an influent waste water stream 12 may be adjusted, if needed, in a tank 14 . High pH may be adjusted downward by the introduction of an acid solution (such as sulfuric) from a tank 16 , or low pH may be adjusted upward by the introduction of a base solution (such as sodium hydroxide or sodium bicarbonate) from a tank 18 . To raise the waste water conductivity, an electrolytic solution (such as sodium sulfate or sodium bicarbonate) may be introduced into tank 14 from a tank 20 . The conductivity also may be raised by introducing an iron component, such as magnetite into the adjusting tank 14 , especially where the precipitates in the effluent water from the EC unit 26 are to be subsequently removed by the EMF unit. Some of the isotopes of concern in the waste water to be treated are transition metal activation products, such as Mn-54, Fe-55, Fe-59, Co-58, Co-60 and Zn-65, and their relatively short-lived decay progeny.
The acid solution may be transferred to the adjusting tank 14 by a metering pump 17 , the base solution by a metering pump 19 , and the electrolytic solution by a metering pump 21 . When the influent waste water is within the desired pH range from 6 to 8, preferably from 6.5 to 7.5, more preferably about 7.0, and the conductivity is in the range of 2 to 1000 μmhos, preferably at least 5.0 μmhos, more preferably at least 20 μmhos, most preferably in the range of 200 to 800 μmhos (tap water being about 200 μmhos), the adjusted waste water is transferred by a pump 24 to an electro-coagulation (EC) unit 26 having a plurality of sacrificial metal anodes 28 connected in parallel to the positive terminal of a power source 30 , and a plurality of cathodes 29 connected in parallel to the negative terminal of the power source 30 .
The waste water fed to the EC unit 26 functions as an electrolyte 34 for carrying a current between the anodes 28 and the cathodes 29 , the amount of this current depending on the conductivity of the waste water and the voltage across the terminals of the power source, which is regulated by a control panel 32 . The amount of current is preferably at least 3 amps, more preferably in the range of 4 to 6 amps. As explained elsewhere, electrolytic reactions and dissolution of the metal of the sacrificial anodes 28 cause coagulation of the dissolved, colloidal and suspended contaminants in the waste water to produce precipitates in the form of floc or sediment. From the EC unit 26 , the thus treated waste water flows to a floc and sediment tank 36 , in which a portion of the precipitants may float as a floe F and a portion of the precipitants may settle out as a sediment S, an intermediate volume between the two being a clarified body of water C.
At this point, the floating flow F may be skimmed off, the clarified water C decanted from the sediment S and sent on for further processing if needed, and the sediment S may be transferred to a dewatering container such as a high integrity container (HIC) with sheet filters and thereafter disposed of in conventional fashion. However, in many cases, further processing of the contents of tank 36 may be preferable to provide an effluent water containing even less contaminants that are present in the clarified water C. For further processing, either or both the sediment S and the floe F may be remixed with the clarified water C and the mixture transferred by a pump 38 to a conventional separation device for separating the precipitates from the waste water, such as a high gradient magnetic filtration unit, an ultrafiltration unit, a microfiltration unit, a dewaterable HIC with sheet filters, or preferably a backflushable filter (BFF), all as represented by the box 40 designated as a conventional filter in FIG. 1 . The filtered precipitates separated from the waste water by conventional filter 40 are then transferred to a conventional radwaste system 42 for disposal. To further enlarge the size of the floc and sediment precipitates and any still suspended precipitates in tank 36 , a flocculation polymer, such as BETZ-1138, may be added to the contents of tank 36 from a supply tank 35 via a metering pump 37 .
Preferably the mixture from tank 36 is transferred by pump 38 to an electromagnetic filter (EMF) unit 44 made and operated in accordance with the invention as described below. When the magnetic field of the EMF is activated by applying to its electrical coils 46 a direct current from a power source 48 , the portion of a ferro-magnetic filtering media bed 50 surrounded by the coil 46 is magnetized and thereby rendered capable of magnetically removing from the wastewater any electro-coagulated precipitates containing a ferro-magnetic component, such as iron containing precipitates where the waste water influent 12 comes from a boiling water reactor (BWR). The ferro-magnetic filtering media bed 50 is made up of a plurality of small ferro-magnetic pieces, preferably small stainless steel balls of a soft, or temporary, magnetic material (e.g. 430 S.S.) that may have a smooth or multi-faceted surface (the former being preferred). The balls are stacked in a tubular housing 52 that is made of a non-magnetizable material and passes through the center of electrical coil 46 . The precipitate containing waste water preferably passes downward through the housing 52 , the media bed 50 and the coil 46 . The effluent from the EMF unit 44 may thereafter be sent to a recovered water tank 54 for discharge or recycle.
While electric current from the power source 48 is passing through coil 46 , the filtering media bed 50 is magnetized and therefore attracts and accumulates the ferro-magnetic precipitates in the waste water influent from floc tank 36 . When the filtering efficiency of the EMF unit deteriorates to an unacceptable level, electrical current to coil 46 is turned off and the filtering media 50 is backflushed with a flow of uncontaminated water from a pump 56 to remove the now demagnetized precipitates from the filtering media bed 50 and carry them into a dewatering component 58 , which is preferably a HIC with sheet filters or a BFF, but also may be another type of conventional filter. The clarified water recovered from dewatering container 58 may then be sent to the recovered water tank 54 for discharge or recycle.
If the effluent from the EC unit as collected in tank 36 contains non-ferro-magnetic species such as cesium (Cs), this species may also be removed by the EMF unit by first adding to the contents of tank 36 a magnetic complexing agent from a magnetic seeding tank 60 via a metering pump 57 . The complexing agent has a ferro-magnetic component. The complexing agent therefore forms a magnetic complex with the non-ferromagnetic species so that the EMF unit may be used for separating the resulting ferro-magnetic complex from the waste water. Where the non-ferromagnetic species is Cs, a preferred complexing agent is as cobalt hexaferricyanate.
As previously indicated, the cathodic reaction involves the reduction of dissolved metal cations to the elemental state so that they plate out as a metal coating on the cathodes 29 . Since at least some of these metals will be radioactive, the cathodes 29 must be periodically regenerated in place by reversing their polarity so that the process anodes 28 become regenerating cathodes and the process cathodes 29 become regenerating anodes to reverse the direction of the current flow and thereby unplate the metal coating from the process cathodes. Pump 24 may be used to provide a fluid flow past the regenerating anodes (i.e., the process cathodes) that serves as a regenerating flush 55 to carry off the unplated metal cations to a conventional radioactive waste disposal system, such as radwaste system 42 .
The details of a preferred embodiment of the EC unit is shown in FIG. 2 , wherein the sacrificial anodes 28 are connected in parallel to the positive terminal of the power source 30 via a positive terminal 62 and a connecting wire 63 . The cathodes 29 , which alternate with the sacrificial anodes, are connected in parallel to the negative terminal of the power source 30 via a negative terminal 65 and a connecting wire 66 . The anodes 28 and the cathodes 29 are mounted on a header or cap 69 so as to be suspended within an electrolyte chamber 68 of a housing 70 , which has fluid inlet 71 and a fluid outlet 72 . The fluid flow through the electrolyte chamber 68 is preferably upward in the direction of arrow 73 , and the flow rate may be in the range of 1 liter per minute (lpm) to 200 gallons per minute (gpm), preferably at least 5 gpm per cell. The housing for a typical cell would be about four to six inches in diameter and about three to four feet long, and would contain about three to four anodes and about three to four cathodes. A typical production unit would comprise about 6 to 12 cells in parallel so that the overall flowrate would be preferably about 30 to 60 gpm for a PWR, BWR, fuel pool, or storage basin. Although an upflow in the direction of the arrow 73 is preferred, the waste water being treated may flow through the housing chamber 68 in either direction. Upflow through the EC unit 26 is preferred both for treatment of the waste water and for cleaning in place the electrodes 28 and 29 because the electrodes are preferably mounted and suspended down from the cap 69 such that there is less interference to fluid flow if that flow enters between the plates at their distal ends.
The EC unit 26 alone will bring down as a precipitate at least 99 percent of the metal contaminants (whether present as ions, colloids and suspended particles) in the waste water influent stream of 12, so that subsequent filtration, preferably by an EMF unit of the type described, will remove from the radioactive waste water substantially all of the contaminants. Testing of an EC unit similar to that shown in FIG. 2 , where measurements were made of the metals content of the influent and of the clarified water (supernate) in a settling container receiving the EC unit effluent, has demonstrated the following removal efficiencies: 99.0% to 99.9% for copper, 99.8% for iron, 99.5% for nickel, and 98.7% to 99.9% for zinc. The demonstrated removal efficiency for total suspended solids was 97.9%.
A preferred embodiment of the EMF unit is shown in FIG. 3 , which shows more clearly than FIG. 1 that the filtering media bed 50 comprises a plurality of small pieces, preferably stainless steel ball bearings 74 , and that the longitudinal centerline of the media housing 52 is preferably aligned with the central axis of the electrical coil 46 surrounding the housing 52 . Ball bearings with smooth round surfaces are preferable for use in the packed bed 50 because such a packed bed has a large void volume, which allows a high loading of ferro-magnetic precipitates. The coil 52 is made up of a continuous electrical conductor 76 that is coiled around a spool 77 . The respective ends of the conductor 76 are connected to the direct current power source 48 via electrical connectors 78 and 79 and their corresponding connector wires. The EMF unit includes a support screen 80 of a mesh size large enough to provide free liquid flow but small enough to prevent passage of the filter media balls 74 . Thus, screen 80 supports the filter media above the outlet 82 of the housing 52 . The unit 44 is connected to the outlet of pump 38 by a conduit 84 and to the recovered water tank 54 by a conduit 87 , which may also include a valve 86 for controlling the rate of fluid flow through the filtering media 50 . The direction of fluid flow through the filtering media bed 50 is preferably downward as illustrated by the arrows 83 and 85 so as to facilitate a subsequent upward backwashing flow that is more effective than a downward flow for removing accumulated precipitates because the heavier crud accumulates at and near where flow enters the bed, and support screen 80 would interfere with using a downward flow to dislodge this crud. However, the EMF unit is also effective for the removal of ferro-magnetic precipitates irrespective of the direction of flow of the waste water being treated or of the backflush water. The rate of fluid flow through the EMF housing 52 may be in the range of 1 lpm to 200 gpm, depending on the overall flow rate through the production EC unit, such that the production EMF unit flow would preferably also be in the range of 30 to 60 gpm.
In FIG. 4 , there is shown a modified EMF housing 52 ′ having an end cap 90 at each end for retaining the filtering media within the housing and for connecting the housing to the influent and effluent conduits. Each housing end cap contains a wall 91 for supporting the filtering media and through which passes a flow tube 92 containing a screening member 93 for preventing passage of the individual pieces of the filtering media. Also shown is a modified filtering media comprised of multifaceted 430 stainless steel balls 74 ′, the facets of which are shown more clearly in FIG. 5 .
In FIG. 6 , there is shown an alternative modification of the EMF unit wherein the filtering media is a 430 stainless steel screen 94 with a 10 micron mesh size, the punched out or woven screen apertures 95 of which are shown more clearly in FIG. 7 . In FIG. 8 , there is shown a further alternative embodiment of the EMF unit wherein the filtering media comprises one or more tubular sheets 97 of 430 stainless steel.
The preferred parameters for electrolytic coagulation of ions and colloids and other solids suspended in radioactive waste water are: adjust waste water pH into range of 5.5 to 8.0, preferably 7.0-8.0, by adding if needed sodium hydroxide or bicarbonate of soda, adjust resistivity to 5 μmhos per centimeter or greater, preferably 20 to 30 μmhos per centimeter (micro-siemens per centimeter, i.e., μmhos are the reciprocal of μohms and may also be referred to as micro-siemens) by adding if need sodium sulfate or sodium bicarbonate, and then apply 4 to 6, preferably 5, amps of direct current (DC) at 23-24 volts. The coagulated floc produced by these parameters can be removed by a 20 to 25 micron filter. Waste water with resistivity of less than 5 μmhos may be adjusted into the desired range by the addition of sodium sulfate or bicarbonate of soda.
The effectiveness of electro-coagulation (EC) may be increased by providing greater electrode contact time by lowering the flow rate or recycling the flow, by increasing the electrode area immersed in the electrolyte, by increasing the current density between the anodes and cathodes, such as by jumpering electrodes of the same type where they are connected in series between the positive and negative terminals (thereby connecting them in parallel), and by raising the conductivity by adding sodium sulfate or bicarbonate of soda.
Because radioactive metals will plate out on the cathode of the electro-coagulation apparatus, it is preferable that these electrodes be cleaned of the deposited metals while remaining in place, instead of being removed for cleaning in a decontamination facility. Such cleaning in place is preferably accomplished by a temporary current reversal during which the EC anode becomes a cathode and the EC cathode becomes an anode to accomplish electro-cleaning. This current reversal causes the plated metals to be redissolved into a waste liquor which is then back flushed to a conventional radioactive disposal system.
The preferred parameters for the magnetic filter is to apply 10 amps of direct current at 36 volts to the conductor coils surrounding the core of stainless steel ball bearings 74 , each preferably having a diameter of about 0.2-0.5 centimeters (cm), more preferably 7/32 inch diameter balls. The stainless steel balls used should serve as a soft magnetic core that does not stay magnetized in the absence of direct current through the surrounding coils. If a hard magnetic core is used, an alternating current must subsequently be applied to the coil to “demagnetize” the hard metal core that would otherwise retain its magnetism.
Since the floc in BWR waster water contains iron, it is magnetic and can be separated from the waste water by the electromagnetic filter. If the amount of ferromagnetic material in the waste water is low, the effectiveness of electromagnetic filtering (EMF) may be enhanced by the addition of magnetite as a seeding agent to the wastewater before it is subjected to electro-coagulation. If the clarified water leaving the combined EC-EMF system has a conductivity that is too high for disposal, reuse or recycle, the conductivity may be lowered by passing the clarified water through an ion exchange system.
The following is an example of the operation of the system of FIG. 1 for the treatment of radioactive waste water containing contaminants in the form of a solution or slurry comprising ions, colloidal particles and suspended solids. The slurry is fed to the adjusting tank 14 , wherein its pH is adjusted from 5.5 to 7 by the addition of sodium hydroxide (or sodium bicarbonate, which adjusts both pH and conductivity) and its conductivity is adjusted from about 2 μmhos to about 100 μmhos by the addition of a saturated sodium sulfate solution or a sodium bicarbonate solution. The lower conductivity would have resulted in negligible current flow between the EC electrodes, whereas the higher conductivity will provide a current of about 4-5 amps. The adjusted influent from the adjusting tank 14 is fed to the EC unit 26 at a flow rate, and the power supply 30 is operated at a voltage, sufficient to apply a current of 1-amp-minute through the waste water as it flows through the EC unit on its way to the floc tank 36 . In the floe tank 36 , sufficient Betz-1138 could be added to provide about 4-10 parts per million (ppm) of this flocculation polymer, which serves to make the sediment S and the floe F in tank 36 significantly larger. However, the EC unit alone is more readily dewaterable due to having less bound water, higher sheer strength, etc.
The thus treated waste water is then conveyed by pump 38 through the EMF unit 44 where this waste water passes through a packed bed of ball bearings made of 430 stainless steel and having smooth surfaces (as most preferred). A current of 7.5 amps is applied to the coils during passage of the waste water through the electromagnetic field generated thereby. The flow rate of this water through the housing 52 , and the axial length of the coil 46 , are such that the residence time of the waste water within the magnetic field is about 2.5 seconds. The effectiveness of this treatment is evident by the visual clarity (clear and colorless) of the EMF effluent delivered to the recovered water tank 54 , as compared with the densely clouded (opaque) suspension of red/brown precipitates of the stirred contents of floe tank 36 as it is fed to the pump 38 . This treated water also has no detectable non-volatile radioactivity (there could still be some volatile tritium gas).
Thereafter, the EMF unit is cleaned by turning off the current and providing a liquid flow reversal through the packed ball core by activating pump 56 to flush away the accumulated floc and convey this floc to a dewatering container 58 , such as a high integrity container (HIC), or some other conventional disposal system for handling radioactive sludges. The deposited settlement from this cleaning liquid will usually meet the EPA's TCLP requirements for disposal, and therefore may usually be sealed in the HIC and shipped to a low level waste site for disposal.
It will be apparent to one of ordinary skill in the art of waste treatment that many other modifications and substitutions may be made to the preferred embodiments described above without departing from the spirit and scope of the present invention as defined by the claims set forth below.
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A method and apparatus for treating radioactive waste water containing contaminating ions, colloids and suspended solids having like (usually negative) charges preventing their precipitation. An electric current is passed through the waste water in an EC assembly to cause electro-coagulation of the contaminants and anodes of this assembly are made of a metal that dissolves to provide cations for neutralizing the negative charges and forming precipitates containing neutralized contaminants. Precipitates are then separated from waste water by an electro-magnetic or other filtering unit. The water pH and conductivity may be adjusted before the EC assembly and additives may be introduced into its effluent for enlargement of precipitate particles, improvement of filtration, improvement of dewaterability, and/or enhancement of magnetism.
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FIELD OF THE INVENTION
[0001] This invention relates to laser diode bars mounted on heat sinks and, more particularly, to avoiding the introduction of defects when soldering laser diode bars to heat sinks.
BACKGROUND OF THE PRIOR ART
[0002] It is current practice to solder laser diode bars to copper heat sinks, sometimes using an intermediate layer of CuW between the diode bar and the heat sink. Because of the wide angle of emission, it is also current practice to mount the emitting edge of the laser bar at the very edge of the heat sink so that none of the emerging rays are blocked. In the soldering operation, the laser diode bar is placed on a solder preform of AuSn atop the heat sink. The assembly is aligned at the emitting edge of the laser bar using a planar datum, clamped together and placed in an oven to reflow the solder Because of the small dimensions involved, the molten solder is liable to flow by capillary action up and over the emitting face of the laser bar, spoiling the light emission from the diode. It would be of great advantage to improve the soldering of laser bars to heat sinks by preventing such unwanted solder overrun.
SUMMARY OF THE INVENTION
[0003] In accordance with the invention, a laser diode bar, solder preform and heat sink are assembled prior to reflowing the solder in a manner to prevent molten solder from being drawn by capillary action over the light emitting end of the diode bar. A pair of recessed alignment pins 37 establish a datum that locates the emitting end of the laser bar, solder preform and an edge of the heat sink without contacting the emitting surface of the laser bar. Advantageously, the recesses in the alignment pins allow the laser bar and solder preform to overhang the heat sink edge by respective amounts. When molten, the solder will not be drawn by capillary action to obscure the light emitting end of the laser diode bar.
BRIEF DESCRIPTION OF THE DRAWING
[0004] The foregoing and other objects and features of the present invention may become more apparent from a reading of the ensuing description together with the drawing in which:
[0005] [0005]FIG. 1 is an isometric view of a prior art laser diode bar mounted on a heat sink;
[0006] [0006]FIG. 2 is an idealized side view of the configuration of FIG. 1;
[0007] [0007]FIG. 3 shows the preferred method of aligning a laser diode bar and heat sink in accordance with the invention; and
[0008] [0008]FIG. 4. is a top view corresponding to FIG. 3.
DESCRIPTION
[0009] Referring now to prior art FIG. 1, a laser diode bar 14 and submount 12 are soldered to a massive heat sink 10 . Laser diode bar 14 typically has a thickness of only 0.005″ and submount 12 , typically made of copper tungsten (CuW) is used to minimize mechanical stress on bar 14 which arises because the thin laser diode bar has a thermal coefficient of expansion (CTE) of about 6 ppm while copper block 10 has a CTE of 16 ppm. A CuW submount 12 which has a CTE similar to that of the laser diode bar. An insulating standoff 15 separates electrode 16 from block 10 . Wires conventionally used to connect electrode 16 to laser diode bar 14 are omitted for clarity.
[0010] An idealized side view of the assembly is shown In FIG. 2. A solder layer 13 secures laser diode bar 14 to submount 12 and a solder layer 11 secures submount 12 to heat sink block 10 . The emitting facet of the laser bar is aligned to the solder preform and the end of the heat sink using a planar datum (not shown). It is customary to use solder in the form of sheets called preforms which are melted when the assembly is placed in an oven to reflow the solder. It should be noted that laser diode bar 14 is soldered so that the diode surface closest to its quantum well layer QW adjoins heat sink 10 . Typical solder preforms may be an 80/20 AuSn or an In alloy.
[0011] When the assembly is connected to a source of electrical power, the emitting facet at the (left-hand) emitting end of quantum well layer QW radiates a beam of laser light that diverges along a “fast axis” and a “slow axis”, the angle “theta fast” of the fast axis being depicted. Ideally, the laser diode facet should be aligned flush with the end of submount 12 and solder preform 13 so that no part of the emitted rays are intercepted or obscured by the submount or solder. To achieve such an alignment, laser diode bar 14 , solder preform 13 , submount 12 , solder preform 11 and heat sink 10 may be placed in a jig so that their left-hand ends are butted against one or more cylindrical alignment pins (not shown). Unfortunately even when properly aligned for the solder reflow operation the molten solder may be drawn by capillary action between the surfaces of the alignment pins and the facet at the emitting end of the laser bar's QW layer, blocking some or all of the laser bar's light output.
[0012] The height of undesired solder rise by capillary flow up the emitting facet is determined by several factors, and may be expressed as:
h = 2 γ lv cos θ ρ gd ,
[0013] where γ lv is the liquid-vapor surface energy;
[0014] θ is the contact angle;
[0015] ρ is the density of the molten solder;
[0016] g is the acceleration of gravity; and
[0017] d is the separation between the surfaces of the alignment pin and the laser bar facet.
[0018] To prevent such capillary action by the reflowed molten solder, the arrangement of FIGS. 3 and 4 is used. FIG. 3 is a side view and FIG. 4 is a top view of a heat sink 30 , a first solder preform 31 , a submount 32 , a second solder preform 33 and a laser diode bar 34 aligned for soldering in accordance with the invention. Laser diode bar 34 is placed on solder preform 33 so that its quantum well layer QW is closest to preform 33 .
[0019] Proper alignment for avoiding capillary action is achieved with the aid of a pair of polished alumina (Al2O3) alignment pins 37 - 1 and 37 - 2 . Alignment pins 37 exhibit three different diameters, 37 a , 37 b and 37 c . It should be noted that this invention teaches that rather than attempting to flush align the end of laser bar 21 with the end of heat sink block 20 , as in the idealized but unachievable alignment depicted in FIG. 2, the alignment pins 37 create a condition where laser bar 34 is deliberately allowed to overhang the ends of heat sink 30 and submount 32 by a minute amount, identified in FIGS. 3 and 4 as “OH 34”. Also, the solder sheet or preform 33 is allowed to overhang the end of heat sink block 30 by a small amount identified as “OH 33” in order to ensure that the solder, when melted, will flow to the end of bar 34 closest to the emitting end. The solder at the end of the laser bar assists in conducting heat away from the emitting facet into the heat sink when the laser bar is in operation. Accordingly, the solder securing the laser bar to the heat sink must extend to the end of the laser bar but must not be permitted to rise up on the emitting facet as solder flow up the emitting facet poses the danger of obscuring the light emitted from the active regions of the facet and thereby degrading laser operation. The amount of solder sheet 33 overhang OH 33 may thus be greater than the amount OH 34 by which laser bar 34 overhangs the ends of submount 32 and heat sink 30 .
[0020] The degree of overhang OH 34 is determined by the difference in diameters of portions 37 a and 37 c of alignment pin 37 . Major diameter 37 a is dimensioned to butt against the left-hand edge of heat sink 30 , solder preform 31 and submount 32 while the diameter of section 37 c is designed to butt against the left-hand end of laser diode bar 34 . It is important that section 37 c not contact the emitting end of the quantum well portion QW of laser bar 34 as established by dimension d2.
[0021] To prevent capillary action obscuring the end of the QW layer, portion 37 b of pin 37 is recessed. The height of the recess portion is identified by dimension d1. The depth of the recessed portion is dimensioned to accommodate the solder preform overhand OH33. Advantageously, the depth of the recess portion is such that solder preform may bottom in the recess when the end of laser bar 34 makes contact with portion 37 c of pin 37 . When the parts are offset as shown in FIGS. 3 and 4, they may advantageously be held in position by a weight W and/or clamp (not shown) to prevent inadvertent movement until the solder is reflowed and allowed to cool to secure the parts together. When the solder sheets are reflowed in an oven (not shown), the portion of solder sheet 33 overhanging the end of heat sink block 30 will be pulled downward by gravity, toward the end of submount 32 , rather than flowing upward by capillary action toward the light emitting facet end of laser diode bar 34 . This safeguards the light emitting end of bar 34 from being overrun by molten solder. Thus, in accordance with the invention, the light emitting end of the laser bar is protected from being obscured by molten solder without resort to any shielding or protective coating.
[0022] In one illustrative embodiment, the following dimensions were employed:
[0023] OH 34=0 to 8μ maximum. (Greater than an 8μ overhand is not desired since it reduces the conduction of heat transfer away from the emitting facet into the heat sink.)
[0024] d1=0.010″.
[0025] OH 33=≅0.001″.
[0026] What has been described is deemed illustrative of the principles of the invention. It should be apparent to those skilled in the art that instead of using recessed pin 30 to locate the ends of the laser bar and solder preforms with respect to an edge of the heat sink, as shown in FIGS. 3 and 4, the overhangs may be accomplished with the use of a “pick and place” machine. It should also be apparent that instead of a solder preform, a predeposited solder layer may be used on the submount and/or heatsink with equally advantageous results. Further, pin 30 may be mounted on a carriage that slides away after the laser bar and submount have been positioned and clamped together before the assembly is placed in an oven to reflow the solder.
[0027] Further and other modifications will be apparent to those skilled in the art and may be made without, however, departing from the scope of the invention.
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A laser diode bar, solder preform and heat sink are assembled prior to reflowing the solder in a manner to prevent molten solder from being drawn by capillary action over the light emitting end of the diode bar. A recessed pin 30 locates the ends of the laser bar and solder preform with respect to an edge of the heat sink so that the laser bar and solder preform overhang the heat sink edge by respective amounts. When molten, the solder will not be drawn by capillary action to obscure the light emitting end of the laser diode bar.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to flash-spinning polymeric film-fibril strands. More particularly, the invention concerns an improvement in such a process which permits flash-spinning of polyethylene strands from a liquid medium which, if released to the atmosphere, Will contain a reduced amount of the trichlorofluoromethane (or "F-11") which has been implicated as a source of depletion of the earth's ozone.
2 Description of the Prior Art
Blades and White, U.S. Pat. No. 3,081,519, describes a flash-spinning process for producing plexifilamentary film-fibril strands from fiber-forming polymers. A solution of the polymer in a liquid, which is a non-solvent for the polymer at or below its normal boiling point, is extruded at a temperature above the normal boiling point of the liquid and at autogenous or higher pressure into a medium of lower temperature and substantially lower pressure. This flash-spinning causes the liquid to vaporize and thereby cool the exudate which forms a plexifilamentary film-fibril strand of the polymer. Preferred polymers include crystalline polyhydrocarbons such as polyethylene and preferred spinning liquids include halocarbons such as F-11
Although F-11 has been a very useful solvent for flash-spinning plexifilamentary film-fibril strands of polyethylene, and has been the solvent used in commercial manufacture of polyethylene plexifilamentary strands, the escape of such a halocarbon into the atmosphere has been implicated as a source of depletion of the earth's ozone. A general discussion of the ozone-depletion problem is presented, for example, by P. S. Zurer, "Search Intensifies for Alternatives to Ozone-Depleting Halocarbons", Chemical & Engineering News, pages 17-20 (Feb. 8, 1988).
An object of this invention is to provide a process for flash-spinning plexifilamentary film-fibril strands of fiber-forming polyethylene wherein the solvent contains a reduced amount of F-11 and the process can be operated without major apparatus modifications to a facility which was constructed for flash-spinning from F-11 alone.
SUMMARY OF THE INVENTION
The present invention provides an improved process for flash-spinning plexifilamentary film-fibril strands wherein polyethylene is dissolved in a halocarbon spin liquid to form a spin solution containing 10 to 20 percent of polyethylene by weight of the solution at a temperature in the range of 130 to 210° C. and a pressure that is greater than 1000 psi which solution is flash-spun into a region of substantially lower temperature and pressure, the improvement wherein the halocarbon spin liquid contains about 20 to about 90 weight percent of at least one isomer of dichlorotrifluoroethane, preferably 1,1-dichloro-2,2,2-trifluoroethane, and about 10 to about 90 weight percent trichlorofluoromethane.
In one preferred embodiment of the invention, the halocarbon spin liquid is an azeotrope of about 22 weight percent 1,1-dichloro-2,2,2-trifluoroethane and about 78 weight percent trichlorofluoromethane.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The term "polyolefin" as used herein, is intended to embrace not only homopolymers of ethylene, but also copolymers wherein at least 85% of the recurring units are ethylene units. One preferred polyethylene is a linear polyethylene which has an upper limit of melting range of about 130 to 135° C., a density in the range of 0.94 to 0.98 g/cm 3 and a melt index (as defined by ASTM D-1238-57T, Condition E) of 0.1 to 6.0. However, other polyethylenes having densities as low as 0.92 and melt index values of up to about 100 can also be used.
The term "plexifilamentary film-fibril strands" as used herein, means a strand which is characterized as a three-dimensional integral network of a multitude of thin, ribbon-like, film-fibril elements of random length and of less than about 4 microns average thickness, generally coextensively aligned with the longitudinal axis of the strand. The film-fibril elements intermittently unite and separate at irregular intervals in various places throughout the length, width and thickness of the strand to form the three-dimensional network. Such strands are described in further detail by Blades and White, U.S. Pat. No. 3,081,519 and by Anderson and Romano, U.S. Pat. No. 3,227,794, the disclosures of which are incorporated herein by reference.
The present invention provides an improvement in the known process for producing plexifilamentary film-fibril strands of fiber-forming polyethylene from a halocarbon spin liquid that contains 10 to 20 weight percent of the fiber-forming polyethylene. A fiber-forming polyethylene is dissolved in the spin liquid to form a spin solution containing 10 to 20 percent of the linear polyethylene by weight of the solution and then is flash-spun at a temperature in the range of 130 to 210° C. and a pressure that is greater than the autogenous pressure of the spin liquid into a region of substantially lower temperature and pressure.
The key improvement of the present invention involves the replacement of a portion of the conventionally used F-11 with at least one isomer of dichlorotrifluoroethane, preferably 1,1-dichloro-2,2,2-trifluoroethane ("HC-123"). The other two isomers are 1,2-dichloro-1,2,2-trifluoroethane ("HC-123a") and 1,1-dichloro-1,2,2-trifluoroethane ("HC-123b").
The following table lists the known normal atmospheric boiling points (Tbp), critical temperatures (Tcr) and critical pressures (Pcr) for the individual halocarbons and for some prior art solvents.
______________________________________ Tbp, °C. Tcr, °C. Pcr, psia______________________________________HC-123 28.7 185 550HC-123a 28HC-123b 30.2Trichloro- 23.8 198.0 639.5fluoromethaneMethylene- 39.9 237.0 894.7chlorideHexane 68.9 234.4 436.5Cyclohexane 80.7 280.4 590.2______________________________________
The HC-123 and its isomers appear to have only a minimal effect upon ozone in the earth's atmosphere. Also it does not appear to suffer from undue toxicity characteristics and it is stable under a wide variety of processing conditions. By replacing a portion of the conventionally used F-11 with HC-123 or its isomers, it is possible to operate a commercial flash-spinning facility without substantial modification and in such a way that when any traces of spin liquid escape to the atmosphere, they will contain a reduced proportion of the F-11 constituent.
A very convenient composition of HC-123 and F-11 is one composed of about 22 and 78 weight percent, respectively, as this is an azeotrope which is easily used and conveniently recovered as such for recycling. However, increasing amounts of the HC-123 or its isomers can also be used, and indeed it is preferred to replace as much of the F-11 as is possible.
The concentration of fiber-forming polyethylene in the spin liquid usually is in the range of 10-20 percent, based on the total weight of the liquid and the fiber-forming polyethylene.
The spin solution preferably consists of halocarbon liquid and fiber-forming polyethylene, but conventional flash-spinning additives can be incorporated by known techniques. These additives can function as ultraviolet-light stabilizers, antioxidants, fillers, dyes, and the like.
The various characteristics and properties mentioned in the preceding discussion and in the examples below were determined by the following procedures.
TEST METHODS
The quality of the plexifilamentary film-fibril strands produced in the examples were rated subjectively. A rating of "5" indicates that the strand had better fibrillation than is usually achieved in the commercial production of spunbonded sheet made from such flash-spun polyethylene strands. A rating of 4"indicates that the product was as good as commercially flash-spun strands. A rating of "3" indicates that the strands were not quite as good as the commercially flash-spun strands. A "2"indicates a very poorly fibrillated, inadequate strand. A "1" indicates no strand formation. A rating of "3" is the minimum considered satisfactory for use in the process of the present invention. The commercial strand product is produced from solutions of about 12.5% linear polyethylene in tichlorofluoromethane substantially as set forth in Lee, U.S. Pat. No. 4,554,207, column 4, line 63, through column 5, line 10, which disclosure is hereby incorporated by reference.
The surface area of the plexifilamentary film-fibril strand product is another measure of the degree and fineness of fibrillation of the flash-spun product. Surface area is measured by the BET nitrogen absorption method of S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem Soc., V. 60 p 309-319 (1938) and is reported as m 2 /g.
Tenacity of the flash-spun strand is determined with an Instron tensile testing machine. The strands are conditioned and tested at 70° F. and 65% relative humidity.
The denier of the strand is determined from the weight of a 15 cm sample length of strand. The sample is then twisted to 10 turns per inch and mounted in the jaws of the Instron Tester. A 1-inch gauge length and an elongation rate of 60% per minute are used. The tenacity at break is recorded in grams per denier (gpd).
The invention is illustrated in the Examples which follow with a batch process in equipment of relatively small size. Such batch processes can be scaled-up and converted to continuous flash-spinning processes that can be performed, for example, in the type of equipment disclosed by Anderson and Romano, U.S. Pat. No. 3,227,794. Parts and percentages are by weight unless otherwise indicated.
EXAMPLES
For each of of the Examples, a high density linear polyethylene of 0.76 Melt Index was flash-spun into satisfactory plexifilamentary film-fibril strand in accordance with the invention.
The apparatus used consists of two high pressure cylindrical chambers, each equipped with a piston which is adapted to apply pressure to the contents of the vessel. The cylinders have an inside diameter of 1.0 inch (2.54×10 -2 m) and each has an internal capacity of 50 cubic centimeters. The cylinders are connected to each other at one end through a 3/32 inch (2.3×10 -3 m) diameter channel and a mixing chamber containing a series of fine mesh screens is used as a static mixer. Mixing it accomplished by forcing the contents of the vessel back and forth between the two cylinders through the static mixer. A spinneret assembly with a quick-acting means for opening the orifice then attached to the channel through a tee. The spinneret assembly consists of a pressure letdown orifice of 0.03375 inch (8.5×10 -4 m) diameter and 0.030 inch length (7.62×10 -4 m), a letdown chamber of 0.25 inch (6.3×10 -3 m) diameter and 1.92 inch length, and a spinneret orifice of 0.030 inch (7.62×10 -4 m) diameter and either 0.020 or 0.030 inches in length. The pistons are driven by high pressure water supplied by a hydraulic system. Pressure transducers are used to measure the pressure before and after the letdown orifice.
In operation, the apparatus is charged with polyethylene pellets and solvents, and high pressure water, e.g. 1800 psi (12410 kPa) is introduced to drive the piston to compress the charge. The contents then are heated to mixing temperature and held at that temperature for about an hour or longer during which time a differential pressure of about 50 psi (345 kPa) is alternatively established between the two cylinders to repeatedly force the contents through the mixing channel from on cylinder to the other to provide mixing and effect formation of a solution. The solution temperature is then raised to the final spin temperature, and held there for about 15 minutes to equilibrate the temperature. Mixing is continued throughout this period. Finally, the spinneret orifice is opened, and the resultant flash-spun product is collected. The pressure inside the letdown chamber recorded during spinning using a computer is entered as spin pressure. For Examples I, II, and III, the letdown chamber was omitted, the pressure was reduced manually to the desired spinning pressure, and the pressure measured just before the spinneret during spinning was entered as the spin pressure.
TABLE______________________________________Example No. I II III IV V______________________________________Solvent CompositionHC-123, % 50 66.7 85 50 22F-11, % 50 33.3 15 50 78MixingTemp., °C. 140 140 140 170 150Press., psig 2800 2800 5500 2000 1800SpinningTemp., °C. 170 170 160 170 170Press., psig 2900 2900 .sup.˜ 5000 1200 .sup.˜ 900Spinneret,DxL, in. 0.030 0.030 0.030 0.030 0.030 × × × × × 0.020 0.020 0.030 0.030 0.030Strand ProductDenier -- -- 639 378 396Tenacity, gpd -- -- 2.7 2.46 2.52Quality 5 4 4.5 4.5 5Surface Area, -- -- 79.2 -- --m.sup.2 /g______________________________________
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An improved process is provided for flash-spinning plexifilamentary film-fibril strands of polyethylene. A portion of the conventionally used trichlorofluoromethane ("F-11") is replaced with at least one isomer of dichlorotrifluoroethane to reduce the ozone depletion hazard.
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BACKGROUND OF THE INVENTION
The present invention relates to the preparation of membranes and their use in effecting enzymatic and biological reactions and separations.
The present invention encompasses a group of matrix membranes, coupling reactions, proteins, enzymes and antibodies, in some respects similar to those of U.S. Pat. Nos. 4,0333,817, 4,033,822 and 4,863,714. As there, there are provided membrane filters to which enzymes and other molecules of similar catalytic or binding activity are attached via chemical bonds, where activation of the pore surfaces of these membranes or filters for purposes of subsequent coupling (where such is needed) can be carried out under pressure-driven conditions, and where the resulting coupled enzyme or biopolymer system can be used under pressure-driven conditions, i.e., by forcing the substrate to be treated through the membrane pores under pressure, to effect useful conversions and separations.
The conventional uses of immobilized biopolymers are well-known in the scientific, industrial and patent literature. The advantages of the immobilization procedure are well-known. The technologies which are usually employed have involved the use of fine particles of either natural or synthetic materials, often of organic polymers or porous materials of other substances, to which enzymes, proteins and other biopolymers are coupled by chemical bonds. These conventional processes have advantages and various disadvantages.
Further, membranes composed of natural polymers such as cellulose or of proteins have been employed, but these are susceptible to degradation or attack by microorganisms and enzymes. A number of purely synthetic membranes have been employed as carriers for protein immobilization, but these are usually not porous membranes but rather in the form of sheets coated with coupling groups, or systems where the active agent such as an enzyme fills the pores and process rates are diffusion-controlled, in large measure.
Still further, polymers of acrylonitrile (PAN) have seldom found use for enzyme immobilization. Where they have, it was under conditions which presented many problems of a preparative nature or in use. For example, proteins have been ionically bound to an acrylonitrile homopolymer after partial derivatization of the nitrile groups to imidoesters; however, only a small amount of protein could be bound. Similarly, amine monomers can be grafted onto PAN polymerized in the presence of bromoform, e.g., the photografting of N,N-dimethylaminoethyl methacrylate, followed by quaternization of the amine and then used via the process of ionic immobilization for the enzyme urease. Further, one can introduce amines into PAN by partial reduction of the nitrile groups; this facilitates the adsorption of proteins which can then be subsequently cross-linked with gluteraldehyde into a stable network. Such supports, however, have limited utility because the activation/coupling chemistries are not versatile and the process results in weak chemical bonds which cannot prevent enzyme leakage due to solvolytic processes.
It is accordingly an object of the present invention to provide ways of immobilizing biopolymers so that they can still engage in biological reactions and interactions to substantially the same extent as the mobile biopolymers prior to immobilization.
It is a further object of the invention to provide a way of producing from acrylonitrile polymers which in membrane form have high versatility and utility.
These and other objects and advantages are realized in accordance with the present invention pursuant to which there are provided novel methods of preparing such membranes, improvements in the coupling chemistries which are employed, and the use of these systems for specific applications of value. Where the system is used as a catalyst for the carrying out of a specific chemical reaction such as the isomerization of glucose, in the manner as described hereinbelow, the system displays a high capacity in terms of its enzyme content and, accordingly, a high enzymatic activity, making this system useful for the large-scale industrial process of glucose isomerization. Enzymes so stabilized have, in addition to the above-mentioned advantages, an intrinsic advantage in terms of a high chemical and thermal stability.
Similarly, when to these membrane filters or ultrafilters are coupled specific ligands, namely substances capable of forming specific complexes with certain species present in a mixture with other substances which may be similar in nature, where the specific agents and ligands are attached by chemical bonds to the inner pore surface of the membrane under pressure-driven conditions, then a process termed affinity sorption, as described in U.S. Pat. No. 4,163,714 can take place, similar to the well known process of affinity chromatography, but possessing unique advantages of speed and convenience. In affinity sorption, the pore diameters and chemical nature of these membranes must be such as to allow for the coupling of a high concentration of ligand, and also to provide for the ready access of the solute molecules whose separation and purification via reversible binding to the ligand substances is desired. The nature of these membranes is such that the excess, undesired components of the mixture can readily be washed out of the membrane or filter under pressure-driven conditions, and then the complex can be dissociated and the desired substance displaced with the effluent in a pure and concentrated state.
Thus, this invention provides new and advantageous ways of effecting separations for analytical and preparative purposes and can be compared with the conventional process of affinity chromatography. Specific advantages of these pressure-driven affinity sorption systems are further set forth in U.S. Pat. No. 4,163,714.
SUMMARY OF THE INVENTION
In accordance with the present invention, we have found that membranes of high capacity, stability and suitability for the binding of various kinds of enzymes and biopolymers can be prepared as is subsequently described.
Specifically, there is provided a series of ultrafiltration membranes based upon synthetic copolymers "tailor made" for specific types of enzyme and protein coupling reactions. The predominant monomer of these copolymers is acrylonitrile (AN) which is the basis for an excellent film-forming polymer, and which can be copolymerized with a wide variety of comonomers. These comonomers include those containing an aryl amine (an amino styrene), a vinyl pyridine or a hydroxyl-containing olefin, e.g., an N-hydroxy-containing-substituent-acrylamide. These can be readily copolymerized with AN and then employed in a variety of activation/coupling chemistries.
The copolymers are dissolved and cast into sheet-like films or as coatings onto particulate matter such as beads, fibers, etc. Then the copolymer is coagulated, i.e., insolubilized. The amine or hydroxy groups are thereafter activated and bound to ligands, enzymes or other biological molecules so as to be capable of use in biological reactions and interactions.
The copolymers, upon coagulation, are in the form of membranes, either sheet-like in the conventional manner or as thin coatings on a carrier. The sizes of the enzyme or biopolymer molecules being coupled to the membranes must be matched to the size of the membrane pores. The size of enzymes and biopolymers can be determined by many techniques, of which calculations based upon the rates of diffusion are but one. The size of the membrane pores is usually determined by the measurement of the relative rates of diffusion or filtration of molecules of a different size. Here, the use of dextran molecules of different sizes is particularly useful. We have found that simple mechanical models suffice as a guide for the preparative procedures used in making the membranes and filters. In effect, the walls of the membranes or filters are lined with enzyme or biopolymer by pumping in solutions thereof from one side of the membrane to the other, after suitable activation. Pores will be blocked unless the pore diameter is at least three times that of the enzyme, protein or antibody. If the feed material contains particularly large molecules which must pass for the purpose of separation or attachment, then membrane diameters considerably larger may be required. One of the important considerations in this invention is the ability to make systems of a specific pore size to fit a specific application.
In order to make use of the pressure-driven concept and where a high capacity is desired, it is important also that the matrix membrane or filter has pores of molecular dimensions so that the system can have a high internal surface for coupling. Membranes having pores of the dimensions of microns are not generally as useful in this regard. The high capacity membranes of this invention usually have pores with diameters ranging from approximately 20 to 200 nm. The matrix membrane must also be capable of withstanding a suitable pressure gradient across it of at least 10 psi on the average, and also be stable at the operating temperature of the system.
Such acrylonitrile copolymeric membranes have found application in certain processes of catalysis, namely conversion of glucose to fructose by an isomerase, as well as in certain areas of separation and purification wherein the affinity sorption principle is used, namely in the removal of desirable substances as part of the fractionation of blood, as well as in affinity sorption as in the separation and purification of antibodies (including monoclonal antibodies) and the parallel use of bound antibodies in affinity sorption processes. The polymers of this invention are usually employed in the form of ultrafiltration membranes but they can also be employed in the form of microporous filters where large pore diamters are needed and a lower capacity is allowed. These polymers can also be used to coat surfaces where a surface reaction suffices for the application.
DETAILED DESCRIPTION OF THE INVENTION
Various high molecular weight copolymers of acrylonitrile and a vinyl comonomer containing an aryl amine, a pyridine, or an aliphatic hydroxyl group have been synthesized via slurry polymerization techniques so as to contain from about 1 to 15 mole percent of functional comonomer.
The teachings of this invention are applicable to a wide range of distinct copolymers of acrylonitrile which can be synthesized to contain one of three different types of functional comonomers. The functional comonomer contained can be either an aryl amine (mAS, pAS), a pyridine (4VP, PEAM), or a hydroxyl group (HOPAM, HOPMAM, HDNMAM). The examples give details of the preparative procedures. Each type of comonomer permits a different activation/coupling chemistry for protein-ligand immobilization.
A variety of factors are involved in choosing a comonomer, the comonomer concentration in the feed, and the polymerization conditions. Considerations include monomer reactivity ratios, availability of comonomers, stability of comonomers and copolymers, copolymer hydrophilicity, as well as the steric availability, the distance of a functional group from the backbone chain of the copolymer. Overriding these considerations in the design of a synthesis, however, is the copolymer's performance in making a membrane of suitable physical/structural stability with the desired porosity. This, in turn, requires producing a polymer of sufficiently high molecular weight without conconmittant gel formation or post-polymerization crosslinking.
For hydroxyl-containing copolymers, the methacrylamide derivatives were found to be superior to the acrylamides. Besides having more favorable reactivity ratios, the methacrylamides gave fewer problems with crosslinking and polymer gelation after dissolution in DMF. Of the two methacrylamides, HDNMAM is a more hydrophilic copolymer than HOPMAM; in addition, the increased length of the spacer arm in HDNMAM is a desirable feature for protein immobilization. However, there is a tendency for a crosslinked gel to form during the polymerization with HDNMAM as compared with the formation of a crystalline glass-like polymer in the syntheses with HOPMAM. This limitation can be overcome by maintaining a low feed concentration of methacrylamide, such as--2 mole % HDNMAM and--5 mole % HOPMAM.
Estimates of the molecular weight of several copolymers can be made from intrinsic viscosity measurements. Such estimates are useful when polymerization conditions need to be adjusted to result in the synthesis of a copolymer with viscosity in DMF appropriate for membrane casting. Since a definite measurement of the molecular weight is not required, concentration terms of order two and higher can be ignored. The dependence of the intrinsic viscosity upon the molecular weight of the copolymer can be assumed to be identical to that of a homopolymer of acrylonitrile.
The intrinsic viscosity of the copolymers in DMF ranged from 89.8 to 298 ml/g, depending on the particular polymerization conditions. Such intrinsic viscosities correspond to a weight-average molecular weight range of 60,000 to 300,000. Copolymers with an intrinsic viscosity of 120 to 200 ml/g were found to be the most suitable for the casting of unsupported membranes of the requisite physical stability and of the desired water permeability.
The copolymer composition can be estimated by UV spectroscopy with the monomer extinction coefficient used as a reference. By UV, the mole ratio mAS/AN in the copolymers is estimated to be about 1.5 times that in the feed. For example, syntheses in which the mole % of mAS in the feed varied from 1.0 to 5.0 resulted in copolymers with a mAS content of 1.8 to 8.5 mole %. The mole content of pAS in the polymer was always less than that in the feed by a factor of about 2 to 3. A feed with 5.0 mole % pAS resulted in a copolymer with 1.9 mole % pAS. Since high molecular weight copolymers of pAS and acrylonitrile are difficult to obtain under the given synthetic conditions, most of the protein immobilizations utilized mAS copolymers.
Syntheses containing from 2.5 to 15 mole % 4VP in the feed resulted in copolymers containing from 3.0 to 20.5 mole % 4VP, respectively. The incorporation levels of 4VP are consistent with the reactivity ratios previously reported.
Acid-base titrations of copolymers containing pyridine or aryl amine functional groups were performed in DMF. The base DTG, when dissolved in DMF, was suitable for the titration of perchlorate copolymer salts.
Acid-base titrations gave, as a rule, a lower comonomer ratio than the UV analysis for the active group. For example, an acrylonitrile-pAS copolymer with 5 mole % pAS in the feed gave 0.84 and 1.6 mole % pAS by titration and UV absorbance, respectively. In contrast, an acrylonitrile-4VP copolymer that contained 10 mole % 4VP in the feed gave 11.7 mole % by acid-base titration and 8.4 mole % by UV absorbance. Such discrepancies may arise from several sources. For example, titration with base may underestimate the true number of functional moieties in a polymer due to the loss of perchlorate during the rigorous washing and drying of the polymer acid salt. On the other hand, estimates based on the UV absorbance are likely to be in error largely due to the assumption of a linear relationship between chromophore concentration and molar extinction coefficient.
The comonomer content can also be quantitated by relative chemical reactivity with trichloro-s-triazine. Films were cast from copolymer solutions, coagulated into unsupported and supported ultrafiltration membranes, and characterized with respect to both water permeability and pore size distribution, the latter by size exclusion chromatography of the membrane permeate of a pool of dextran fractions. These ultrafiltration membranes can be used for protein immobilization after appropriate chemical activation. The three distinct types of functional copolymers give comparable results for alpha-chymotrypsin, as an example, with protein weight loadings of 6 to 12 percent and 40 to 65% retention of enzymatic specific activity.
The invention will be further described in the following illustrative examples wherein all parts are by weight unless otherwise expressed.
The following chemicals were purchased from Aldrich Chemical Co. and the abbreviations have the indicated meanings: 3-(a-hydroxyethyl)aniline (HEA), 4-(2-aminoethyl)pyridine, 4-ethylpyridine, m-ethylaniline, p-ethylaniline, acryloyl chloride, methacryloyl chloride, 2,6-di-tert-butyl-4-methylphenol (BHT), trichloro-s-triazine (TsT), N,N-diisopropylethylamine (DIPEA) and 1,3-di-O-tolylguanidine (DTG). Acrylonitrile, 2,2'-azobis(2-methylpropionitrile) (AIBN) and p-methoxyphenol (MEHQ) were obtained from Eastman Kodak Co. Other chemicals and their vendors include: alumina F1, 14-28 mesh (Alcoa Chemical); N,N-di-2-naphthyl-p-phenylene diamine (Pfaltz & Bauer); N-(9-hydroxy-4,7-dioxa-nonyl)amine (polyglycolamine H-163, from Union Carbide); triethylamine, acetic anhydride, ethylenediamine (EDA), ethylene carbonate (EC), propylene carbonate (PC), N,N-dimethylformamide (DMF), and cyanogen bromide (Fisher Scientific); acrylic acid (Dow Badische Chemical Co.); polyacrylonitrile, (PAN, type A homopolymer, from DuPont); 2-(2-aminoethoxy)ethanol (diglycolamine, from Texaco Chemical Co.); 4-vinylpyridine (4-VP, from Reilly Tar & Chemical Co.); p-aminostyrene (pAS, from Fairfield Chemical Co.); and, Amberlite IRA-900 and IRC-50 (Rohm & Haas). Bovine a-chymotrypsin (CT), blue dextran, e-amino-n-caproic acid (EACA), glutaryl-L-phenylalanine-p-nitroanilide (GPNA), and dextran fractions of average molecular weight 10,500, 17,700, 40,000, 70,300, 252,000, and 2,000,000 were supplied by Sigma Chemical Co. A dextran fraction of molecular weight 4,000 to 6,000 was obtained from Accurate Chemical. Polystyrene calibration standards were the products of Waters Associates or Polysciences Inc. Acrylonitrile (AN) was freshly distilled before use after being made acidic with phosphoric acid.
Also from Aldrich was purchased 2-methoxy-4,6-dichloro-s-tsiazine (MDsT). Glucose isomerase (GI) was obtained from Miles-Kali Chemie.
Also obtained were Staphylococcus aureus (Cowan strain) protein A (PA), protein A-Sepharose CL-4B, bovine serum albumin (BSA), bovine alpha-chymotrypsin (CT), glutaryl-L-phenylalanine-p-nitroanilide (GPNA) and globulin-free human serum albumin (HSA) from Sigma Chemical Co; soybean trypsin inhibitor (STI) from Worthington Biochemicals; human immunoglobulin G (IgG) and medium electroendosmosis agarose from Miles Laboratories; Rabbit anti-human serum albumin antisera (anti-HSA qG) was obtained from Cappel Laboratories or Miles Laboratories.
Certain abbreviations are employed in this invention to refer to certain materials. For example, the polymer of AN is referred to as PAN, while the copolymer of AN and m-aminostyrene is referred to as P(AN-mAS).
EXAMPLE 1
Synthesis of m-aminostyrene (mAS).
mAS was prepared by a protocol modified from one for pAS. HEA (50 g) was melted at 80° C. and added dropwise to 50 ml of solid alumina granules heated to about 300° C., 12 torr, in a 3-neck round bottom flask equipped with a heated addition funnel, a thermometer, and a water condenser/receiving flask; the receiving flask contained 3.5 mg of the non-volatile polymerization inhibitor, N,N-di-2-naphthyl-p-phenylene diamine. Care was taken to avoid an excessive rise in temperature during the addition of HEA onto the alumina. The product was removed from the starting material, inhibitor, and water by vacuum distillation at 20 torr through a Vigreaux column. The colorless product in a 50% yield was collected at 54° C. and stored at -20° C. Reverse phase ion-pair chromatography on a Sperisorb-C6 column showed that over 98% of the material absorbing at 280 nm eluted in one peak, with only a minor non-absorbing peak as detected by refractometry.
EXAMPLE 2
Synthesis of N-(5-hydroxy-3-oxa-pentyl)methacrylamide (HOPMAM), N-(5-hydroxy-3-oxa-pentyl)acrylamide (HOPAM), and N-(9-hydroxy-4,7-dioxa-nonyl)methacrylamide (HDNMAM).
Three hydroxy-containing vinyl monomers were synthesized by minor variations on the following scheme. A mixture of 500 ml absolute ethanol, 1.0 mole (101 g) triethylamine, 0.2 g MEHQ, and 1.0 mole (105 g) diglycolamine (or 1.0 mole, 163 g, polyglycolamine) was dried thoroughly over 3A molecular sieves and filtered through a 0.45 mm cellulose acetate membrane filter into a 3-neck round bottom flask equipped with an addition funnel, thermometer, and a nitrogen inlet. The flask was cooled to -50° C. by immersion in a dry ice/alcohol bath while under a nitrogen atmosphere; 1.0 mole of methacryloyl chloride (105 g) or acryloyl chloride (90.5 g) was then added slowly, accompanied by overhead mechanical stirring. After the temperature was allowed to increase to -20° C., a triethylamine-HCl precipitate was removed by filtration through paper on a jacketed Buchner funnel maintained at -10° C. The filtrate was pooled with a 100 ml -20° C. ethanol wash of the precipitate and passed through an Amberlite IRA-900 column to remove chloride ions. The effluent was checked for the absence of chloride ions with 1% AgNO 3 in 1N HNO 3 . After rinsing the column with ethanol, 0.2 g of MEHQ was added to the column effluent/wash pool which was subsequently concentrated on a rotary evaporator to about 160 g; this concentration step also removed residual triethylamine. The concentrate was diluted with 250 ml of ethanol and repurified by passage through an Amberlite IRC-50 column to remove residual amines. The effluent was pooled with a 250 ml ethanol rinse of the column and, after the addition of 0.2 g MEHQ, it was concentrated and dried under high vacuum. The yield was between 80 and 85% for all three acrylamides.
EXAMPLE 3
Synthesis of N-(2-(4-pyridyl)ethyl)acylamide (PEAM)
This substituted acrylamide was synthesized from acrylic anhydride and 4-(2-aminoethyl)pyridine. Acrylic anhydride was obtained from acrylic acid and acetic anhydride. Synthesis of PEAM was initiated by the slow addition of 0.36 mole (45.0 g) of acrylic anhydride in 50 ml of ethyl ether containing 50 mg of BHT to 0.35 mole (42.76 g) of 4-(2-aminoethyl)pyridine in 150 ml of ethyl ether containing 150 mg of BHT at -55° C., with the formation of a precipitate. The rate of addition was kept sufficiently slow to ensure that the temperature did not exceed -30° C. during the reaction. After removal of the ether by room temperature evaporation, the precipitate was dissolved in 200 ml of methanol and subsequently vacuum distilled. The substituted acrylamide (15% yield) was collected at 170° C., 100 mtorr.
EXAMPLE 4
Copolymerization of Acrylonitrile with N-Substituted Acrylamides, N-Substituted Methacrylamides, or 4-vinylpyridine
These copolymerizations were performed as an aqueous slurry at pH 3.2 with a total monomer concentration of 1.4M. The reactions were done under nitrogen in a resin kettle equipped with a turbine stirrer and an internal cooling coil. A reaction was initiated by the addition of ammonium peroxydisulfate (0.02% final concentration) and sodium metabisulfate (0.1% final concentration); the temperature was thermostatted at 50°+0.3° C. An 80% conversion was typically achieved by 2 to 3 hours. The polymer was isolated by vacuum filtration, washed with water (or 1.0M NH 4 OH for a pyridine containing copolymer), dispersed in a blender, collected again by filtration, and dried at 50° C. under vacuum.
EXAMPLE 5
Copolymerization of Acrylonitrile with m-- or p-Aminostyrene.
Copolymerization was performed in 50% methanol using AIBN as the initiator. For example, 3.0 g pAS was dispersed in 120 ml of water and concentrated HCl was added until the amine dissolved fully. The solution was then treated with activated charcoal to remove colored contaminants. After filtration to remove the charcoal, the pH was adjusted to 1.1 with concentrated HCl, and 125 ml of methanol was added. The solution was transferred to a 3-neck round bottom flask equipped with a subsurface nitrogen inlet, a thermometer, a mechanical stirrer, and a reflux condenser. Distilled acrylonitrile (65 ml, 53 g) and 150 mg AIBN was added with stirring; the system was purged with nitrogen throughout. The temperature was then brought to and maintained at 50° C. The reaction proceeded rapidly and after 20 hours, 50 ml of 50% methanol was added to thin the slurry. After a total of 48 hours, 50 ml of 1.0M NH 4 OH was added and the polymer collected by filtration. Following blending in 1.0M NH 4 OH and washing with ethanol, the polymer was dried under vacuum at 40° C. A 70% conversion was typical.
To yield a viscosity suitable for membrane casting, polymers can be dissolved in DMF using extensive mixing with a magnetic stirrer; in some cases, mechanical blending may be employed to decrease the viscosity of the polymer solution to a level suitable for casting. After filtration through Whatman #4 paper, thin films can be spread onto dry chromic acid-washed glass plates with an 8 mil (203 mm) gate opening on a casting knife; this, followed by immediate aqueous coagulation at 2° to 5° C., will minimize skin formation. Hydroxyl, aryl amine, and pyridyl polymer films were coagulated in deionized water, 0.1M, HCl, and 0.1M NH 4 OH, respectively. Polymer solutions can be stored at either ambient temperatures (hydroxyl polymers) or -20° C. (aryl amine and pyridyl polymers). Membrane sheets can be stored in 10 mM HCl, 0.02% NaN 3 at ambient temperatures. Care should be taken to minimize the exposure of the amine polymers and membrane sheets to light.
Membrane thickness can be measured with a Peacock dial gauge, while membrane water content can be estimated, after a quick dry-blotting of surface moisture, by weighing, drying in a vacuum oven, and reweighing of the dry membrane. Water flux can be measured at 50 psi (345 kPa) of N 2 on 47 mm diameter membrane disks supported by a non-woven, porous poly(ethylene terphtalate) cloth (Hollytex 3396 from Eaton-Dikeman.)
Assuming that a membrane consists of an ensemble of identically sized cylindrical pores and that Poiseuille's law is applicable, an estimate of a membrane's average pore radius is calculated from
r=(8hlU/pDAK).sup.0.5
where,
r=pore radius in cm;
h=solution viscosity in poise;
1=membrane thickness in cm;
U=rate of fluid in ml/min;
p=pressure in atm;
D=void volume of membrane in %;
A=membrane area in cm 2 ; and
K=a units conversion factor of 6.08×10 7 .
Membranes can be cast onto a support such as Hollyex (Eaton-Dikeman) using the same general procedures, and the properties of the final films resemble those of comparably-cast unsupported membranes except that, since the coagulation solvent attacks the cast films from both faces, the pore structures are somewhat different.
Preparation of membranes is illustrated in the following examples:
EXAMPLE 6
Preparation of P(AN-HOPAM Membrane)
P(AN-HOPAM) polymer from Example 2, of intrinsic viscosity 298 ml/g and with a mole ratio of AN:HOPAM 9:3 in the feed, was dissolved in DMF to concentrations of 6, 9, 12 and 15 w/v%. These were cast at a gate opening of 7 mils onto glass plates and the plates were immediately thereafter immersed in water at room temperature and then further water washed to remove all soluble material. Disks were then cut from the cast sheets and their properties were measured. The results obtained are set forth in Table 1.
TABLE 1______________________________________Properties of P(AN-HOPAM) MembranesMembrane 6.0 9.0 12.0 15.0______________________________________Thickness (μm) 92 102 110 112Percent Solids 11.3 12.9 15.1 20.1Dry Weight/Membrane Area 8.0 11.5 16.8 23.2(g/m.sup.2)Water Permeability 285 230 95 75(μm sec.sup.-1 atm.sup.-1)Pore Size Radius (nm) 49.0 46.5 32.0 29.0______________________________________
EXAMPLE 7
Preparation of P(AN-4VP Membranes)
The process of Example 6 was repeated with one of the copolymers of Example 4 of intrinsic viscosity 133 m/g and a mole ratio in the feed of AN:4VP of 90:10. UV absorption gave the composition as a 85:15 mole ratio.
The results obtained are shown in Table 2.
TABLE 2______________________________________Membrane 7.0 9.1 11.9 14.0______________________________________Thickness (μm) 97 98 104 105Percent Solids 9.5 11.5 15.1 17.6Dry Weight/Membrane Area 9.2 11.7 16.1 19.4(g/m.sup.2)Water Permeability 925 700 530 295(μm sec.sup.-1 atm.sup.-1)Pore Size Radius (nm) 89.5 79.0 72.5 55.0______________________________________
EXAMPLE 8
Preparation of P(AN-mAS Membranes)
The polymer from Example 5 with an intrinsic viscosity of 198 ml/g and a molar ratio in the feed of AN:mAS of 96:4, was dissolved in DMF to a concentration of 10% w/v and cast as in Example 6, except that the coagulation liquid was 0.1M HCl in water.
Proteins, enzymes, antibodies, and the like, can be covalently attached to membranes after appropriate activation of the functional monomer in each copolymer. Pyridine containing membranes were activated with cyanogen bromide, while aryl amine and hydroxyl containing membranes can be activated with TsT in dioxane. EDA can be coupled to activated hydroxyl containing membranes in dioxane to prevent hydrolysis of triazinyl-chlorides. The amount of EDA coupled to a membrane can be measured by ninhydrin analysis of dried membrane fragments, using EACA as a standard.
The following examples illustrate membrane activation:
EXAMPLE 9
Trichloro-s-Triazine Activation
TsT and MDsT were recrystallized from ligroin and stored in a dessicator protected from light. The activation of the aryl amine P(AN-mAS) from Example 6 membrane with TsT or MDsT was initiated by the passage of 50 ml of 0.1M NH 4 OH, followed by placing the membrane in a filtration funnel and passage therethrough of two successive 100 ml portions of 99% p-dioxane, and finally of 25 ml of 0.05M TsT or MDsT in p-dioxane supplemented with 0.1M DIPEA. The membrane was then removed from the filtration funnel and gently stirred in 75 ml of the same solution for 30 to 45 minutes at ambient temperature. Each activated membrane was subsequently soaked for 10 minutes in p-dioxane, remounted in the filtration funnel and flushed successively with 50 ml of p-dioxane and 50 ml of acetonitrile. Displacement of dioxane (m.p 11.8° C.) by acetonitrile was necessitated by the low temperature of the subsequent protein coupling reactions.
EXAMPLE 10
Diazotization of Aryl Amine Membranes
The conversion of the aryl amine membrane of Example 8 to a diazonium salt was effected under N 2 pressure by passage through the membrane, in a filtration funnel, of 25 ml of ice-cold 0.5M acetic acid followed by 25 ml of ice-cold 0.3M NaNO 2 in 0.5M acetic acid. After incubation in the same ice-cold solution for 30 minutes, the membrane was washed under pressure with successive ice-cold 10 ml portions of 0.1M sulfamic acid and enzyme coupling buffer.
EXAMPLE 11
Cyanogen Bromide Activation of Pyridyl Copolymer Membranes
The membrane of Example 7 containing pyridyl groups was activated by the successive passage therethrough of 50 ml of 0.1M NH 4 OH, and two 50 ml volumes of p-dioxane, followed by the cycling of 20% (w/v) CNBr in p-dioxane for 10 minutes. The CNBr reagent was washed out with three 50 ml volumes of p-dioxane, followed by 50 ml of deionized water.
CT can be coupled to activated membranes at pH 8.5 in aqueous buffer. Solvent changes and membrane washings can be accomplished at 50 psi by the mounting of a membrane in a stainless steel pressure filtration funnel (Gelman Science). Enzyme activity of immobilized CT can be measured under continuous pumped-flow conditions at pH 8.5 with GPNA as a substrate. The protein loading of a membrane can be determined by ninhydrin analysis of an acid hydrolysate of a dried membrane, or quantitation of tryptophan in a base hydrolysate of a membrane.
As noted, proteins, such as alpha-chymotrypsin (CT), glucose isomerase (GI) and Protein A can be immobilized to the membranes after appropriate chemical activation. The most frequently used activation methods are: trichloro-s-triazine on the aryl amine membrane for the coupling of CT; diazotization on the aryl amine membrane for the coupling of GI. The weight loading for CT is about 6 to 12 percent with 40 to 65 percent retention of enzymatic activity. These results are typical of those obtained with ultrafiltration-type membranes. Membranes of higher porosity yeilded less loading but were of comparable activity.
The following examples illustrate coupling:
EXAMPLE 12
Chymotrypsin Coupling Procedures
CT was coupled to the TsT and the MDsT-activated membranes of Example 9 by the pressurized flow therethrough of 25 ml of ice-cold coupling buffer (0.1M Na HCO 3 , pH 8.5, 0.1M NaCl), followed immediately by three passages of 15 ml of CT (10 mg/ml) in ice-cold coupling buffer. The membrane was then immersed and incubated in the same CT solution overnight at 4° C. Subsequently, the membrane was washed by the sequential pressurized flow therethrough of 75 ml of: coupling buffer; 1.0M ethanolamine, pH 8.0; 0.1M Tris.HCl, pH 9.4, 1.0M NaCl; 0.1M Na acetate, pH 4.0, 1.0M NaCl; 0.1M Na HEPES, pH 7.0, 0.1M NaCl, 0.02% NaN 3 . The CT-coupled membranes were stored at 4° C. in the final wash buffer or in 1 mM HCl.
CT was attached to CNBr-activated pyridyl membranes and diazotized aryl amine membranes as described above, with the substitution of 0.5M NH 4 Cl and 0.1M HEA in coupling buffer, respectively, for the ethanolamine solution.
EXAMPLE 13
Glucose Isomerase Coupling
GI was coupled to TST and to MDsT-activated membranes at pH 8.5 and pH 5.0, respectively. The former was identical to Example 12 except that it used 10 ml of GI solution at a concentration of 0.5 to 3.0 mg/ml. Coupling at the lower pH employed a buffer of 0.1M Na acetate, pH 5.0, 0.1M NaCl. Washing of GI-coupled membranes was done successively with 50 ml coupling buffer, 50 ml of 1.0M ethanolamine in coupling buffer, coupling buffer supplemented with 1.5M NaCl, 50 ml coupling buffer, and finally 50 ml of reaction buffer (0.1M Na maleate, pH 6.8, 0.1M NaCl). GI activated membranes were stored at 4° C. in reaction buffer supplemented with 0.02% NaN 3 .
The coupling of GI to CNBr-activated pyridyl membranes and diazotized aryl amine membranes was comparable to that used for CT, in Example 9, but with a concentration of GI as mentioned above. Washing also was as mentioned in Example 12 with the appropriate substitution for the ethanolamine step.
EXAMPLE 14
Protein A and Bovine Serum Albumin Coupling
PA was coupled to pyridyl membranes via CNBr and to arylamine membranes via MDsT by passing through the membrane an 0.5 mg/ml solution of 0.1M NaHCO 3 , 0.15M NaCl, pH 8.5; the filtrate was collected and recycled through the membrane five times. Membranes were then incubated overnight at 4° C. in the protein coupling solution, washed and stored at 4° C. in 0.1M HEPES, 0.15M NaCl, pH 7.0.
A control membrane to which a neutral, non-binding protein was coupled was also prepared, using pyridyl membranes via CNBr and also aryl amine membranes via MDsT. Control membranes were prepared to measure the non-specific adsorption or entrapment of protein on membranes. A protein which did not serve as an affinity ligand, in this case BSA, was coupled to an activated membrane. BSA was attached by passing a 3.0 mg/ml and a 20.0 mg/ml BSA solution in pH 8.5 coupling buffer through 13 mm and 47 mm membrane disks, respectively, and incubating as previously described.
The following examples illustrate the use of the coupled membranes in enzymatic conversion and affinity sorption:
EXAMPLE 15
Glucose Conversion
For glucose conversion, purified GI from Streptomyces albus, covalently immobilized as described in Example 13, with 10 percent weight loading and 50 to 70 percent retention of enzymatic specific activity was employed. The activity of membrane-bound GI was assayed at 70° C. in pH 6.8 maleate buffer containing 0.3M glucose, 7 mM MgSO 4 , and 3 mM CoSO 4 . Fructose formation was determined via cysteine-carbazole assay. The GI reactor containing a single 47 mm diameter membrane disk operated in a single pass flow mode at a flow rate of 0.5 ml/min and resulted in 10% conversion; up to 20% conversion was observed with higher flow rates. A Co +2 concentration of 0.4 and 3.0 mM was necessary for optimal thermal stability of soluble and immobilized GI, respectively. The GI-membrane reactor had a half-life of about 150 hours. The K m and the V max for the immobilized GI were about 0.25M and 15 μmol/min-mg, respectively; these are slightly lower than and comparable to, respectively, those for soluble GI. When the flow rate was increased, a maximum level of activity was observed, at which diffusion control of the rate of reaction no longer existed. Diffusional limitations were insignificant at flow rates of at least 3 ml/min with a substrate concentration of 0.3M glucose.
For a continuous flow reactor at the chosen optimum cobalt concentration, a flow rate of 0.46 ml/min and a single-pass flow mode was operated continuously for 9 days. The half-life of the CFR was 150 hours. The reactor operated continuously at 0.45 ml/min in single-pass flow mode at 70° C. with maleate buffer containing 0.3M glucose.
The activity-pH profile of membrane-bound GI showed a quite broad peak, with 80% activity at pH 6.5 compared to 20% for the free enzyme, which suggests that practical operation at the more desirable, lower pH is possible with the membrane-bound enzyme. Peak activity is, in both cases, at pH 8.0.
The advantages of the membrane-bound GI system operated under pressure-driven conditions include the observation that the activity of the bound enzyme reached its peak at 85° C. with a rather flat plateau from 75°-90° C., while the native enzyme's activity peaked sharply at 70° C., was one-third of that at 65° C. and fell sharply at 80° C. Also, the pressure-driven reactor showed an activity which rose sharply with flow rate, reaching its maximum activity at quite reasonable flow rates and pressures depending on the hydraulic permeability of the membrane selected, so diffusion was not rate-limiting for this system. The intrinsic rate constants for the reversible conversion processes were found to agree rather well with those for the soluble enzyme. The properties of the bound enzyme systems showed overall advantages in terms of allowable pH and temperature ranges while being capable of rapid conversion rates.
The affinity sorption biospecific purification of biopolymer was also achieved, that of trypsin inhibitor and immunoglobulin G were effected by the forced flow of solutions containing these proteins through ultrafiltration membranes containing immobilized chymotrypsin or Protein A, respectively. Soybean trypsin inhibitor (STI) was also bound to chymotrypsin-containing membranes (0.75 g active enzyme/m 2 ) at pH 7 and 0.1 g/m 2 of protein eluted with urea at pH 2. Protein A binding species of IgG were analogously purified from serum albumin-IgG mixtures, with a yield of 0.5 g IgG/m 2 of membrane. The Protein A membranes were reuseable over a period of one month with no loss in binding activity. Flow through the pores of the membrane was laminar at the flow rates employed, and, the shear forces associated with such flow rates were shown not to be sufficient to disrupt an IgG-Protein A complex. Thus, the teachings of this invention can be compared to two common affinity chromatography purification systems employing bead systems, namely the binding of soybean trypsin inhibitor to immobilized a-chymotrypsin and the binding of the F c segment of immunoglobulin G to immobilized Staphylococcus aureus Protein A, The membranes of this invention showed that they could be used advantage for these purification and separation processes, and are a viable, highly efficient and rapid alternative to column methods.
For the affinity sorption purification-separation procedures, use was made of pyridyl membrane disks of 47 mm diameter reacted for 30 minutes with 0.1M CNBr in dioxane, followed by a wash with water to cleave the pyridine rings into two reactive aldehyde groups; also used were aryl amine membrane disks activated with 50 mM 2-methoxy-4,6-dichloro-s-triazine, 100 mM N,N-diisopropylethylamine in dioxane. CT was coupled as described in Example 12. The coupling of PA and BSA are described in Example 14.
The following example illustrates the affinity sorption of STI to immobilized CT:
EXAMPLE 16
Affinity Sorption of Soybean Trypsin Inhibitor to Chymotrypsin
For the affinity sorption of immobilized STI to CT, the enzymatic activity of immobilized CT was initially determined in a continuous flow GPNA assay. Membranes were then assayed for the binding of STI under convective flow conditions in a vacuum filtration system which consisted of a rotary vane vacuum pump, 125 ml filtration flasks, 47 mm diameter in-line polycarbonate filter holders (Gelman Sciences), syringe resevoirs, Tygon tubing outlets, and 5 ml polystyrene tubes placed inside the filtration flasks to collect eluates. Membranes were washed with 100 ml of binding buffer (50 mM Tris-HCl, 5 mM CaCl 2 , pH 8.0) in a stainless steel filtration funnel at 50 psig before they were placed the in-line filter holders.
In the binding assay, 8 ml of a 0.30 mg/ml solution of tritiated STI in binding buffer was applied under a slight vacuum (2.7 psia), recycled through the membrane three times, and then allowed to incubate in the permeate overnight at 25° C. STI which may have bound non-specifically was eluted with 90 to 110 ml of wash buffer (50 mM Tris-HCl, 5 mM CaCl 2 , 1.5M NaCl, pH 8.0) at 1.5 ml/min; the CT bound STI was eluted with 25 ml of elution buffer (8.0M urea, 0.1M NaCl, pH 2.0 with HCl) at 0.75 ml/min. Because of a decrease in the membrane flux upon the binding of STI, a higher vacuum (13.7 psia) was used throughout the wash and elution steps. Eluate fractions of 1 ml were collected and mixed with 5 ml of scintillation cocktail for counting on a Beckman Model LS 7000 liquid scintillation counter. Lastly, the enzymatic activity towards GPNA was remeasured and the protein loading of a membrane was determined by the assay of base hydrolysates for tryptophan.
The results are shown in Table 3.
TABLE 3______________________________________Binding of STI to Membranes Containing CTor a Non-Specific Ligand STI STIMembrane Applied mg of STI Eluted at RecoveredLigand (mg) pH 8.0 pH 2.0 (%)______________________________________CT 3000 1893 164 73.5BSA 2400 2160 26 94.2______________________________________
STI was thus bound to competent molecules of immobilized CT by the forced convective flow of a STI solution through the membrane's pores. An excess of STI was provided during the binding stage so that the maximum amount of complex formation would result. Biospecifically bound STI was found to elute with urea at pH 2.0. Because of the high ratio of pore surface area to membrane volume and the large CT loading on a membrane, all binding occurred in a compact volume (a residence times of 7-14 sec. at the elution flow rates). Because of this compactness, the interface of pH change moves through the membrane with little dispersion; this is not the case for large columns where back-mixing occurs. This unique and advantageous feature of this membrane system allows the affinity bound material to elute off in a smaller volume, in this case 20 ml.
The affinity sorption procedure applied to the separation and purification of antibodies, including monocloved antibodies, made use of immobilized PA membranes as described in Example 17. Here IgG antibodies were employed. The elution of IgG from a PA-membrane based on the P(AN-4PV) copolymer of Example 14 was accomplished with a residence time 17-fold less than that required with a CT-membrane at the same flow rate. Since this complex does not involve a covalent bond, IgG is expected to dissociate faster than STI and elute in a smaller volume. This was observed for PA membranes. The excess IgG in the loading buffer was eluted in 10 ml of pH 7.0 buffer, while biospecifically bound IgG eluted in less than 5 ml of pH 3.0 buffer. Less than 1 mg of IgG was detected in the wash fractions prior to the change in pH. As was the case with STI, the highest concentration of IgG was found in the first acid fraction. Nevertheless, less than 20 ml was required to completely elute all non-bound and bound IgG.
EXAMPLE 17
Affinity Sorption of IgG to PA
Immobilized PA membranes from Example 14 were placed in 13 mm in-line filter holders and used in the vacuum filtration system of Example 15. The membranes were washed with IgG binding buffer (50 mM Na phosphate, 150 mM NaCl, pH 7.0) before passage of 2.5 ml of IgG binding buffer containing 0.4 mg/ml of 3 H-IgG. After passage through the membranes three times at a flow rate of about 0.10 ml/min, the membranes were incubated in the final permeate overnight at 4° C. Then, the membranes were washed with 15 ml of binding buffer and affinity-bound IgG was eluted at pH 3 with 5 ml of IgG elution buffer (0.1M Gly-HCl, 1.5M NaCl, pH 3). Permeate fractions were collected and counted as previously described. Table 4 summarizes the results obtained with coupled PA membranes alongside these coupled BSA membranes for purposes of comparison.
TABLE 4______________________________________Binding of IgG to Membranes Containing PA or BSA. Mem- IgG mg of IgG IgGMembrane brane Applied Eluted at RecoveredType Ligand (mg) pH 7.0 pH 3.0 (%)______________________________________unsupported PA 651 476 40.9 79.3mAS-AN PA 1100 886 42.7 84.4 BSA 651 582 2.5 89.8 BSA 1100 970 4.2 88.6Unsupported PA 1034 850 59.6 88.04VP-AN BSA 1034 894 18.9 88.3Supported PA 947 725 57.1 82.74VP-AN BSA 947 781 39.8 86.7______________________________________
Duplicate mAs-An membranes were assayed for IgG binding at two different concentrations. The tabulated entries are the average of two identical membranes. The membranes were washed with pH 7 buffer to remove non-specifically bound IgG and with pH 3 buffer to elute affinity bound IgG. The specially bound IgG was about 40 μg for both membrane types of the unsupported variety. The support makes for a substantial amount of non-specific sorption.
To demonstrate a practical use of these PA membranes, the affinity absorbancy of IgG out of a mixture of proteins was performed. If IgG is to be isolated directly out of serum without a prior separatory step, then large excess of serum albumin must not prevent IgG-PA complex formation. To show this, a mixture of BSA and human IgG with a 32:1 weight ratio of BSA to IgG was applied to PA membranes that were initially analysed for IgG binding from a homogeneous IgG solution. Following this, the membranes were washed extensively and analysed again for IgG bonding fron a homogeneous IgG solution. As long as sufficient IgG was present to saturate the PA ligands the binding capacity was substantially unchanged. When insufficient IgG was present for saturation and a large excess of BSA was present, there was some loss in IgG capacity probably due to loose, non-specific binding of BSA to PA and steric hinderance, but the IgG present was readily isolated from the mixture. A repeat uptake of pure and sufficient IgG showed the original PA capacity.
The strength and stability of the IgG-immobilized PA complex was also observed under forced convective flow with pH 7 buffer and with a protein solution through the membrane. It was found that the shear forces applied by pressure-driven affinity sorption cycles did not disrupt the PA-IgG complex nor did non-interacting proteins (BSA) compete with PA in eluting IgG from the membrane. Thus, the applicability of this system to blood processing was demonstrated.
For certain applications of the affinity sorption, it may be necessary to treat solutions or even fine suspensions which have in them so many large molecules or particles that the fine pore membranes customarily employed in ultrafiltration will not accommodate these materials. In other cases the actual complex to be formed is itself quite large and here also a fine pore membrane is not suitable simply on the basis of pore size.
Several solutions are available. The matrix copolymer membrane could be cast with a suitable porosity but this is often difficult to achieve while still maintaining adequate physical strength and there is the further disadvantage that many small pores of high adsorptive capacity are also formed to make for non-specific adsorption because they are not available for ligand coupling. Since the copolymers of this invention lend themselves very well to the coating of existing woven and nonwoven fabrics as well as polymeric surfaces, the preferred embodiment of this invention in these cases involves coating pre-existing fabric materials with the copolymer or coating an appropriate surface and then effecting the appropriate sequence of activation-coupling-sorption processes. Many fabrics including ones of polyester and nylon can be readily coated. With a judicious selection of solvents and the methodologies well known to those skilled in the art, coatings which are strongly adherent and cover the entire exposed surfaces are readily achieved. The speed of the sorption process is very high and no limitations of functions due to the presence of formed bodies obtain, particularly when solid surfaces are employed as in the classical "dipstick" procedure.
Example 17 describes another affinity sorption procedure, that which applies to the removal of fibronectin (FN) from a human plasma cryoprecipitate, as could be practiced in blood processing. FN is a non-enzymatic adhesive glycoprotein which binds strongly to certain substances and has itself a high molecular weight of 440,000 so it requires a highly available binding surface. Example 18 describes an affinity sorption system for FN.
EXAMPLE 18
Affinity sorption of Fibronectin By Coupled Gelatin Membrane
To an arylamine copolymer activated with TsT as described in Example 9 there can be coupled a gelatin fraction having an average MW of 16,000, carrying out the reaction at 35° C. to keep the gelatin in solution and provide for substantial binding of that ligand. An artificial cryoprecipitate, FN mixed with BSA, can be then passed through this immobilized gelatin filter employing a pH 7.4 buffer, following which the filter is washed with the same buffer. Then an eluting solution containing guanidine-HCl is used to desorbe the FN in concentrated solution.
Another application of affinity sorption to blood processing based on the specific reactions demonstrated by antibodies was demonstrated by the use of a coated fabric affinity sorption system for the binding of an antigen, in this case HSA, to an antibody, in this case Anti-HSA IgG or (ASG), to an immobilized PA filter. Here a three component complex is formed with PA bound directly by activation to the copolymer surface coating, itself treated with the antibody specific to the antigen HSA, and then the antigen removed from a complex mixture by affinity sorption. Depending upon the strength of the various complexes between PA and the antibody and between the antibody and the antigen, it may be necessary to effect a chemical coupling of the antibody to TA as is readily achieved by the familiar glutaraldehyde reaction.
EXAMPLE 19
Affinity Sorption by a PA membrane-ASG Complex of an Antibody
An immobilized PA filter was made by coating a fabric with polymer followed by the coupling of PA as described in Example 14, and then 3 ml of a 0.1 mg/ml solution of Rabbit anti-HSA IgG can be passed through to the PA as described in Example 16. At that point 3 ml of 0.25 mg/ml of tritiated HSA in IgG binding buffer is applied to the membrane followed by membrane washing, elution and counting as previously described. Substantial amounts of the antigen, in this case HSA, can be desorbed from the filter and concentrated thereby.
The problem of non-specific hydrophobic adsorption as interfering with the rate and sharpness of the separations to be achieved by affinity sorption processes has been documented earlier in this invention. Many means are available within the teachings of this invention for the amelioration or even elimination of this problem. AN copolymerizes also with a number of hydrophilic monomers including ones carrying the sulphonic acid group and others carrying the amide or similar hydrophilic groups. Monomers based upon acrylamide substituted with quarternary ammonium groups are also known. Terpolymers of AN together with a hydrophobic monomer and one of the three classes of copolymers employed for coupling could be prepared by those skilled in the art and these could serve to reduce the hydrophobicity of copolymers which are largely made up of AN. The introduction of hydrophilic monomers reduces the mechanical strength and increases the swelling of the resulting material, so there are several, basic limitations on the extent to which mixtures can be employed.
One of the techniques of this invention is the employment of specific combinations of polymers, coupling chemistries, ligands or enzymes, and the like, to accomplish specific processes to substantial advantage. In this light, it will be appreciated that the instant specification and the examples are set forth by way of illustration and not limitation and that various modifications and changes may be made without departing from the spirit and scope of the present invention.
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A membrane is produced by dissolving, in a water-miscible solvent, a water insoluble copolymer of acrylontrile with at least one monomer selected from the group consisting of an aminostyrene, a vinyl pyridine and an N-hydroxy-containing-substituent-acrylamide, casting said solution to form a thin layer of solution, contacting said solution with water thereby to coagulate the copolymer into a film, and washing away from the copolymer film the solution of solvent and water. The amine or hydroxy group of the copolymer is then activated and coupled with a ligand such as glucose isomerase, chymotrypsin or Protein A. The coupled membranes can then be used for biological separations and reactions.
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TECHNICAL FIELD OF INVENTION
[0001] The present invention relates to a method for continuous production of solid, hollow or open profiles, in particular those including sharp edges, by extrusion of thermoplastics, polystyrenes in particular.
BRIEF DISCUSSION OF RELATED ART
[0002] Polystyrene profiles with a density larger than 400 kg/m 3 have been produced for many years, for use in interior or exterior decoration of dwellings. These profiles with various shapes have a pronounced decorative aspect and are often used for replacing or imitating decorations of stucco ceilings. Further, by their high density, they are able to withstand impacts, which allows their use at the level of circulation of persons and mobile objects which may knock them. As polystyrene does hardly absorb any water, such profiles may be used at ground level, as plinths.
[0003] In order to be able to produce profiles with complex decorations of good quality and having an acceptable surface aspect, it is required that the profile have a regular structure, i.e., fine and uniform cells. If the cells are irregular, surface defects are visible and the profiles are not marketable.
[0004] In spite of many efforts, it has not been possible to produce such polystyrene profiles with a density less than 400 kg/m 3 . Indeed, as soon as producing profiles with a density less than this value is attempted, structures are obtained which are not sufficiently regular to obtain profiles which do not have interfering surface defects.
[0005] U.S. Pat. No. 5,753,717 describes a method for extruding polystyrene foam by means of CO 2 , having an improved mechanical strength, obtained by attaining a temperature at the outlet of the die, less than a critical temperature. To successfully cool the polymer+CO 2 mixture below this critical temperature, the inventor emphasizes the necessity of jointly injecting a larger proportion of foaming agent. Density is consequently lowered, the gas having a reduction effect on the viscosity by plasticization, which reduces viscous frictions and heat generated by these frictions. The described obtained products are in the form of sheets, intended to be thermoformed, having a particularly fine cell size (<25 μm) and a cell wall thickness from 1 to 2 μm. The density of the foam is less than 4 lbs/ft 3 (64 kg/m 3 ].
[0006] Moreover, U.S. Pat. No. 5,753,717 emphasizes that it has previously not been possible to obtain polystyrene foams with high densities AND a very fine cell size: by reducing the proportion of swelling agent, density increases but the cells become thick and large. U.S. Pat. No. 5,753,717 further specifies that with the conventional prior method, only sheets of foams with rather large and thick cells may be obtained by working at die temperatures of at least 140° C. and up to 155° C.
[0007] U.S. 2002/0169224 describes a continuous method for preparing foams having reduced and/or uniform cell sizes by forming a uniform mixture of polymer and foaming agent, by reducing the temperature of the mixture at the outlet and at a sufficient pressure in order to maintain the foaming agent in the solution and by subsequently having the mixture pass through an outlet port before expanding it. The extrusion temperature is equal to or less than 30° above the glass transition temperature of the polymer and the amount of CO 2 used is at least 4.4% by weight of the Polymer. The claimed cell sizes are between 2 and 200 μm and the densities between 100 and 300 kg/m 3 .
BRIEF SUMMARY OF THE INVENTION
[0008] The invention proposes a new method for producing profiles comprising polystyrene foam with a density between 200 kg/m 3 and 350 kg/m 3 , with fine cells from 25 to 100 μm and with a homogeneous size.
[0009] This is achieved by a method for producing solid, hollow or open profiles, in particular those including sharp edges, based on polystyrene, including the following steps:
dosing polymers comprising polystyrene and optionally other additives and adjuvants plasticizing the components in an extruder in order to obtain a homogenous mixture, injecting a pressurized gas via an injection port in an amount from 0.2 to 0.4% by weight based on the polymers comprising polystyrene. kneading and pressurizing said homogeneous mixture and gas until complete dissolution of the gas in order to obtain a mixture in a single phase, gradually cooling said mixture while maintaining the pressure required for solubilizing the gas, up to a temperature above 135° C., giving rise to the intended density and cell size, said temperature preferably being as uniform as possible in a cross-section perpendicular to the flow, in order to minimize differences in temperature between the centre and the perimeter of the polymer and dissolved gas flux, having said mixture pass as a single phase mixture, into a shaping tool in order to form a foam, having the thereby formed foam pass through an optionally temperature-controlled calibration system, drawing the calibrated foam with a motor.
[0018] Polystyrene-based foams with a density between 200 kg/m 3 and 350 kg/m 3 while having a smooth surface aspect and without any apparent defects may be produced with this method,
[0019] By means of the control, the efficiency and homogeneity of the applied cooling, the method allows an increase in the productivity of profiles and the quality of the cells is well uniform.
[0020] Surprisingly, foams with a density between 200 kg/m 3 and 350 kg/m 3 , with fine cells from 25 to 100 μm, and with a homogeneous size, may be obtained by the method developed within the scope of the present invention, even with optimum foaming temperatures above 135° C.
[0021] In the case of the present invention, given that the aimed densities are much higher than those contemplated in U.S. Pat. No. 5,753,717, the thickness of the cell walls will inevitably be larger. But obtaining sufficiently fine cells in order to provide the foams of the present invention with an adequate surface quality, remains essential, and this seemed difficult or even unfeasible according to U.S. Pat. No. 5,753,717. The analysis of the possible causes of these problems led us to consider not only the cooling power to be applied, the temperature to be attained at the die but also the homogeneity of this temperature in a section perpendicular to the flow. The more it is desired to achieve high densities, the larger is the cooling power to be achieved, but especially the more it is difficult to reduce the difference in temperature between the centre of the flux and the edges. This then results in that the too hot centre of the flow will have a lower viscosity, providing less resistance to expansion of gas bubbles, thereby increasing the average size of the cells of the foam, to the detriment of its aspect and quality.
[0022] The optimum temperature at which the foam reaches the most favorable quality (density−cell size) is also crucial, for this the cooling system should be sufficiently powerful, nevertheless gradual and well-controlled.
[0023] According to a first advantageous embodiment, the applied polymer is selected from the group consisting of polystyrene, acrylonitrile-butadiene-styrene (ABS), styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEBS) or mixtures thereof.
[0024] Several kinds of polystyrenes which differ in viscosity, and therefore in molecular weight, may also be used alone or mixed with other copolymers of styrene and a diene monomer. Adequate copolymers are for example acrylonitrile-butadiene-styrene (ABS), styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEBS) or mixtures thereof.
[0025] It is also possible to alter a portion or all the surface of the solidified primary foam profile by adding a further layer of material to it by co-extrusion. This co-extruded material may be in the foamed or compact state.
[0026] The foaming gas preferably used is CO 2 .
DETAILED DESCRIPTION OF THE INVENTION
[0027] Other particularities and features of the invention will become apparent from the detailed description of a few advantageous embodiments presented hereinbelow, as an illustration.
[0000] 1. Manufacturing Method:
[0000] 1.1. Dosage of the Components:
[0028] The components of the formulation are individually dosed by a volumetric or gravimetric type dosage station, in order to specifically achieve the desired composition. The raw materials preferably are in the form of regular granules, if possible with the same size and the same shape from one component to the other. It will also be preferred that the apparent density be in a narrow range between the different components, in order not to cause premature demixtion.
[0000] 1.2. Extruder:
[0029] The thereby dosed components are conveyed towards the feeder of a plasticizing extruder. This extruder preferably includes two co-rotary or counter-rotary screws, either self-cleaning or not. The cylinder includes several heating zones. The first portion of the cylinder is heated at a high temperature, in order to plasticize the solid components dosed at the feeder, while kneading them to homogenize the whole. At the most favorable location from the viscosity and pressure point of view, in the cylinder, pressurized gas is injected via an injection port bored into the cylinder. The gas will be maintained in its condensed phase, in particular, in the supercritical state in the case of CO 2 (see point 2.2). The mixture of the components and the gas is kneaded and pressurized in order to obtain good homogeneity and optimum dissolution of the gas in the molten mixture so as to obtain a single phase. The cylinder zones are then gradually colder in order to maintain the pressure required for solubilizing the gas.
[0000] 1.3. Cooling:
[0030] It may be achieved by two arrangements:
i) A “dynamic” heat exchanger by using a configuration with long screws: as the first portion of the cylinder has been used for plasticizing and homogenizing solid components with the gas as described in the previous point b), the second portion of the screw, the zones of which are cooled by the flow of a coolant fluid, provides the cooling of the monophase mixture. The design of the screw of the latter portion is specifically adapted to generate the least possible heat by shearing, which increases the potential cooling capacity and therefore benefits productivity. The design of the cooling section of the screw will be adapted so as to achieve at the inlet of the die the optimum temperature, with the homogeneity of which in a cross-section perpendicular to the flow, it is possible to obtain the advantageous claimed combination of density and cell size. ii) A “static” heat exchanger: the homogeneous mixture of the plasticized components+the gas leaves the cylinder of the extruder so as to pass through a heat exchanger, through which a coolant fluid flows, the design of which should provide control over the mixing temperature to within a tenth of a degree, so that the optimum foaming temperature at the die may be obtained with the the desired accuracy and graduality. The exchanger should further be designed in order to smooth out the temperature profile in a cross-section perpendicular to the flow, in order to make the temperature profile at the exit of this exchanger, as flat as possible. By adding a static exchanger after the cylinder of the extruder, it is further possible to increase the permissible flow rate.
1.4. Homogenization:
[0033] The cooled mixture is optionally again homogenized, by having it pass into a static mixer which will divide the flux into several “channels” which will be crossed and redistributed, in order to make the temperature profile of a perpendicular section of the flux as flat as possible.
[0000] 1.5. Relaxation:
[0034] A section for relaxation of the flux may optionally be added, by placing an empty tube over a suitable distance. This allows the internal stresses due to shearing, as well as visco-elastic “memory” effects to be released and to provide a more regular flow of the flux.
[0000] 1.6. Foaming Die:
[0035] The monophase mixture, homogeneous in composition and in temperature, of the plasticized components and the gas will now pass into the shaping tool, consisting of a die guiding the flux towards the intended foaming shape. The pressure drop undergone by the mixture from the outlet of the cylinder constantly reduces the pressure of the mixture; at one moment, this pressure drops below the critical threshold where the previously solubilized gas will oversaturate the mixture and gas bubbles will then originate, forming a second discrete phase. Ideally, the zone where these primary bubbles form should not be passed too early, otherwise pre-foaming may occur giving a deformed and unstable foam with a not very attractive surface. The measures of actions on the location where this critical demixing step occurs, are multiple: viscosity of the components, temperature of the tool, proportion of gas, shape of the tool, throughput of the extruder . . . all these parameters should be optimized for each foam profile to be achieved.
[0000] 1.7. Shaping:
[0036] The foam emerges into the atmosphere, at a high temperature, and freely expands. The viscosity of the cell walls increases with cooling, and migration of the gas into the cells, until the cell structure is set. But this process takes time, and the shape of the foam is not immediately stable. In order to control the dimensions of the foam, it is passed through a calibration system, by drawing it by a motor at the end of the extrusion line. The calibrators, possibly temperature-controlled calibrators for more efficient control of the shape, especially at the beginning when the foam is the hottest, gradually impose to the foamed mass, its definitive shape.
[0000] 1.8. In-Line Co-Extrusion (Optional):
[0037] It is possible to alter a portion or all the surface of the solidified primary foam profile by adding by co-extrusion an additional layer of material thereto. This secondary layer, which should compatible with the first in order to provide good cohesion, may have the function of reinforcing the mechanical properties, a decorative effect, . . . the secondary layer may be compact or foamed.
[0000] 1.9. In-Line Ornamentation (Optional):
[0038] It is possible to print decorative patterns on a selected portion of the profile, for example via a heating roll pressed against the locally preheated foam, or by a press system advancing with the profile, or any other method known to one skilled in the art.
[0000] 1.10. Drawing and Cutting Operation:
[0039] The foam is therefore drawn by a simple or dual powered drawing machine according to the number of profiles extruded in parallel. The profile is then cut to length by a saw, providing a really perpendicular cut.
[0000] 1.11. Off-Line Ornamentation (Optional):
[0040] It is possible to print decorative patterns on a selected portion of the cut-out profile, for example via a heating roll pressed against the locally preheated foam, or by a press system advancing with the profile, or any other method to one skilled in the art.
[0000] 2. Raw Materials:
[0000] 2.1. Polymers:
[0041] Polystyrene is used as a base resin. The viscosity of the polystyrene will be adapted according to the foam profile, to the pressure required for obtaining good quality, to the desirable extrusion throughput. Several kinds of polystyrenes, differing in viscosity and therefore in molecular weight, with flow indexes (“Melt Flow Rate” MFR), from 1 to 25 g/10 minutes, according to ASTM D1238, measured at 200° C. and with a load of 5.0 _kg, may be used alone or as a mixture. Copolymers of styrene and a diene monomer, which have a better impact strength and better elasticity, may also be added. For example: suitable acrylonitrile-butadiene-styrene (ABS), styrene-butadiene-styrene (SBS), styrene-ethylene-butadiene-styrene (SEBS), also having variable flow indexes (“Melt Flow Rate” MFR), according to the foam to be obtained.
[0042] Recycled material, compatible with all the components, for example scraps of foamed profiles, milled, degassed, and densified beforehand may also be added.
[0043] In the case of a co-extruded layer on the base foam, the materials are selected according to whether they are able to form a sufficiently cohesive bond with the base foam. These may be thermoplastics, thermosetting materials.
[0000] 2.2. Gas:
[0044] The gas used is preferably CO 2 , stored in a pressurized tank and at a temperature such that it is in the liquid state. By no means should 31.1° C. be exceeded, beyond this temperature, CO 2 becomes supercritical and therefore has a significantly lower density than the liquid, which makes its pumping delicate. The CO 2 is pumped in conduits cooled to significantly below the critical temperature, in order to maintain the liquid state up to the device for controlling the injection flow rate. This is a flowmeter operating according to the Coriolis effect, which allows the mass of the dosed gas per unit time to be linked to a difference in vibration velocity induced by the passage of the fluid in a vibrating conduit. As this flowmeter only works for liquids, it is therefore essential that the CO 2 remains in this state. The liquid CO 2 is then brought into the cylinder of the extruder via in injection port provided with a non-return valve.
[0000] 2.3. Additives:
[0000]
a. Nucleating Agent:
[0046] The cells of the foam are regularized by using a compound which will promote homogeneous distribution of the cells in the foam. These may be passive products, which do not react chemically, such as talc, calcium carbonate, silica, . . . So-called “active” products may also be used which will decompose under the action of heat by giving off a gas phase. The reaction promotes homogeneous nucleation, as well as the presence of domains of finely divided gas. The combinations of citric acid and sodium bicarbonate, azodicarbonamide, OBSH, . . . , are well known.
b. Additives assisting the process:
[0048] These are compounds facilitating extrusion of the polystyrene mixture, by an internal or external lubrication effect. This is generally a molecule having a low molecular weight. Among the known products, let us mention esters of C4—C20 mono-alcohols, fatty acid amides, polyethylene waxes, oxidized polyethylene waxes, styrene waxes, C1—C4 alcohols, siliconized compounds, etc. These compounds may either be added to the mixture as soon as it enters the extruder, either as a master polystyrene-based mixture, or injected as a liquid into the extruder, or even injected with regularity and accuracy at the suitable location of the extrusion tool via a distributor ring, in order to exclusively and regularly line the flow channel of the die so as to form a film with a very low friction coefficient.
c. Pigments:
[0050] The foam mass may be uniformly colored by using pigments added to the feeder of the extruder. It is also possible to obtain a “wood effect” by using associations of color pigments with very different viscosities, for example combining a bright colored master mixture based on a high viscosity polymer with a dark colored master mixture based on a low viscosity polymer.
d. Other Additives: Let us further mention unexhaustively:
Fire retardants, either halogenated [chlorinated, brominated, fluorinated, . . . ] or not [hydroxides, phosphates, expansible graphite, . . . ]; UV stabilizers; Antioxidants; Various mineral fillers; Strengthening fibers (glass, cellulose, . . . ) Additives acting on the melt viscosity (high molecular weight acrylic copolymers)
3. EXEMPLARY EMBODIMENTS
[0059] The following examples illustrate the conditions for obtaining the representative foams of the invention and their morphological aspects. The key extrusion parameters, the dimension of the profiles and the extracted amount of heat during cooling, are grouped in a table.
[0060] The polymer used is a crystalline polystyrene, MFI=15. A nucleating agent of the citric acid+sodium bicarbonate type was added in order to control the size of the cells. The foaming gas is 100% CO 2 .
[0061] When a heat exchanger is used (Examples Nos. 1 to 5), the extracted amount of heat is calculated in order to reach the optimum die temperature. In the absence of an exchanger (Example No. 6), with no access to the temperature of the mass in the cylinder before the cooling section, it is not possible to evaluate this amount of heat. However, the optimum extrusion temperature is indicated.
Example No. 1 2 3 4 5 6 Dimensions W × I mm × mm 120*15 40*20 38*16 150*17 19*12 40*20 Current volume/meter dm 3 /m 1.26 0.42 0.39 2.23 0.2 0.42 Density kg/nm 3 344 311 295 343.6 308.2 297 Exchanger? YES YES YES YES YES NO PS mass flow rate kg PS/h 120 90 80 130 50 80 CO 2 mass flow rate g CO 2 /min 4.8 4.6 4.1 5 2.9 4.3 CO 2 concentration weight % 0.2 0.3 0.3 0.2 0.4 0.3 Exchanger inlet T° ° C. 192 189 188 193 184 — Die T° ° C. 154.8 157.4 163.5 156.9 161.6 159.5 DELTA T° 37.2 31.6 24.5 36.1 22.4 — Cooling power kJ/h 8225.87 5242.82 3613.21 8647.36 2065.20 —
[0062] It is seen that the amounts of heat are logical according to the densities, dimensions and extrusion rates. Examples 2 and 3 however illustrate that the optimum extrusion temperatures at the die also are a function of the complexity of the shapes: in spite of their similar volumes, the shape of Example 3 is much more tortuous than that of Example 2, increasing frictions, but the method in each case is sufficiently adaptive and flexible so that foams with a regular and fine cell structure may be obtained.
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The invention relates to a method for producing solid, hollow or open profiles, in particular those including sharp edges, based on polystyrene, including the following steps: dosing polymers comprising polystyrene and optionally other additives and adjuvants plasticizing the components in an extruder in order to obtain a homogenous mixture, injecting a pressurized gas via an injection port kneading and pressurizing said homogenous mixture and gas until complete dissolution of the gas in order to obtain a mixture in a single phase, gradually cooling said mixture as a single phase in order to maintain the pressure required for solubilizing the gas, having said mixture pass as a single phase mixture, into a shaping tool in order to form a foam, having the thereby formed foam pass through an optionally temperature-controlled calibration system, drawing the calibrated foam with a motor.
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This application claims priority to my earlier filed provisional application Ser. No. 60/334,405, filed on Dec. 3, 2001.
FIELD OF THE INVENTION
This invention relates generally to catalytic heaters and more particularly to a method of preheating catalytic heaters.
BACKGROUND OF THE INVENTION
In a catalytic heater, heat is produced when a gaseous fuel is brought into contact with a catalyst in the presence of air containing a normal level of oxygen. Typically, the fuels are natural gas, propane and butane, for example.
Generally, the combustible gas or fuel is fed through the bottom of the catalytic heater and is dispersed at atmospheric pressure into contact with a porous active layer. This layer contains the catalyst which may be platinum, for example. Oxygen from the atmosphere enters the porous catalytic layer and reacts with the gaseous fuel, promoted by the catalyst. This reaction releases the BTU content in the fuel in the form of radiant energy. Catalytic heaters are therefore used as a source for infrared heat. The chemical reaction that occurs during the oxidation reduction process produces temperatures within the catalyst of from about 500 to 1000 degrees Fahrenheit (F). The actual temperature at the surface of catalytic heater is dependent upon the rate at which the fuel gas is introduced to the catalyst. The surface of the heater is typically rectangular or circular and ranges from about one square foot to about 10 square feet. The volume of the gas delivered to the catalytic surface may range from about 2 to 6 cubic feet of gas per hour per square foot.
Before a catalytic heater can be operated successfully, the heater and more particularly the catalyst must be preheated to a temperature at which the oxidation reaction can be sustained. At the present, most all catalytic heaters use an electric resistance tubular heater (calrod) to preheat the platinum catalyst before the gas is introduced into the heater. However, some manufactures of catalytic heaters are attempting to use methods of preheating the catalyst other than with an electrical element. These methods include a flame pilot light that impinges the internal or external surface of the catalyst, raising its temperature high enough for the catalyst to flamelessly oxidize the incoming gas fuel. Another method consists of ducting hot air in close proximity to the catalyst, raising the temperature sufficiently to react the incoming gas fuel.
SUMMARY OF THE INVENTION
It has been discovered in accordance with the invention that the temperature of the catalyst in a catalytic heater can be effectively raised to the required level to react with an incoming fuel by contacting the catalyst with a gaseous mixture composed essentially of hydrogen and nitrogen. It has been found that mixing the hydrogen with nitrogen effectively lowers the temperature of reaction with the catalyst, creating a safe method for preheating the catalyst.
Further, in accordance with the invention, it has been discovered that to be most effective the gaseous mixture should be maintained in a volume ratio of between about 95% hydrogen to about 5% nitrogen and about 5% hydrogen to about 95% nitrogen at ambient conditions. Preferably, although not necessarily, the gaseous mixture of hydrogen and nitrogen may be introduced into the catalytic heater through the existing gas inlets that are employed to control the heater in normal operation.
More specifically then, the invention provides a new and improved method of preheating a catalyst in a catalytic heater comprising the steps of:
preparing a gaseous mixture of hydrogen and nitrogen in a volume ratio of between about 95% hydrogen to about 5% nitrogen and about 5% hydrogen to about 95% nitrogen at ambient conditions, and
dispersing the gaseous mixture into contact with the catalyst for a period of time sufficient to raise the temperature of the catalyst to a level that will promote the flameless oxidation of a fuel gas in the presence of the catalyst at ambient conditions.
The catalyst is preferably a platinum catalyst incorporated within a porous insulating layer. The porous insulating layer is exposed on one side to the ambient atmosphere and on the opposite or interior side to the flow of fuel gas from a suitable dispersing medium. The dispersing medium may be a dispersion plate having a plurality of substantially equally spaced apart holes for uniformly dispersing the gaseous mixture and fuel gas into contact with the insulating layer containing the catalyst. The gaseous mixture and fuel gas may be supplied through a plenum chamber located at the bottom of the catalytic heater. The plenum chamber is provided with the necessary inlets for introducing both the gaseous mixture and fuel gas.
It has been further found in accordance with the invention that the starting gaseous mixture can be most effectively and uniformly distributed into contact with the catalyst by passing the mixture through a porous baffling medium, such as an open metal mesh or screen, positioned between the dispersion plate and the porous insulating layer. The baffling medium serves to distribute the gaseous mixture evenly over the whole area of the catalyst-containing insulating layer so that the entire catalyst can be quickly and most efficiently brought to operating temperature before the fuel gas is introduced.
BRIEF DESCRIPTION OF THE DRAWING
In the accompanying drawing:
FIG. 1 is a partially cut-away, perspective view of a section of a catalytic heater showing the gas inlet manifold system used for feeding the fuel gas into the catalytic heater as well as the preheat or starting gas mixture in accordance with the invention; and
FIG. 2 is a cross-sectional view of the body or frame portion of the catalytic heater showing the construction of the plenum chamber, dispersion plate and baffling medium for distributing the fuel gas to the interior of the heater.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawing, there is shown a catalytic heater of a preferred type to which the preheating method of the invention is particularly suited. As shown, the catalytic heater comprises a body or frame 10 of a somewhat “Z” shaped configuration having an open end 12 and an opposite end 14 closed by a back plate 16 . Disposed within the open end 12 is an insulating layer 18 incorporating a catalyst, such as platinum, along with an open grill 20 made of stainless steel, for example, which is mounted on top of the insulating layer 18 . Below the insulating layer 18 is a metal dispersion plate 22 having therein a plurality of tiny holes 24 substantially uniformly spaced apart over the surface of the plate. The dispersion plate 22 is spaced apart from the back plate 16 a suitable distance to form a sealed plenum chamber 26 . A gas inlet 28 is provided within the back plate 16 to allow for the passage of a fuel gas, such as natural or propane gas, for example, from a suitable supply, such as a gas tank 30 .
The fuel gas is fed from the supply through a main operating valve 32 and a conduit 34 connected to the gas inlet 28 via a hose pipe 36 , for example. The fuel gas enters the sealed plenum chamber 26 at a predetermined pressure and is substantially uniformly disbursed throughout the insulating layer 18 by the plurality of holes 24 in the dispersion plate 22 and contacts the catalyst. Oxygen from the atmosphere enters the heater through the open end 12 , passing through the grill 20 and the insulating layer 18 and reacts with the gaseous fuel, promoted by the catalyst, at substantially ambient conditions. This reaction releases the BTU content in the fuel in the form of radiant heat.
Before the radiant heat producing reaction can occur, it is necessary to preheat the catalyst to a temperature which is high enough for the catalyst to flamelessly oxidize the incoming fuel gas. In the past, as indicated above, this has been achieved by use of an electric resistance heater or a flame pilot light, for example.
It has been found in accordance with the invention that a gas mixture composed of substantially pure (e.g. 99%) hydrogen and nitrogen can be used to start a catalytic heater before the fuel gas is introduced. The starter mixture when introduced into a catalytic heater safely raises the catalyst temperature to the required level to react with the incoming fuel gas to start the heater. Hydrogen gas has a unique property in that when it comes into contact with platinum at room temperature, it will instantly oxidize with the platinum, releasing heat. The reaction is generally so violent that a stream of 99% pure hydrogen impinging on the catalyst will create a temperature on the catalyst that causes the hydrogen stream to burn, the auto ignition point of hydrogen being about 800 degrees F.
It has been discovered, however, in accordance with the invention that this reaction can be safely tempered for use in preheating a catalytic heater by mixing the hydrogen with nitrogen in a predetermined volume ratio and then feeding the mixture into contact with the catalyst. The volume ratio of hydrogen to nitrogen in the mixture should be between about 95% hydrogen to about 5% nitrogen and about 5% hydrogen to about 95% nitrogen at ambient conditions. Preferably, the volume ratio is maintained between about 60% hydrogen to about 40% nitrogen and about 40% hydrogen to about 60% nitrogen at ambient conditions. In actual practice, the volume ratio may often vary depending upon the ambient and seasonal conditions. For example, during the winter months, the preferred volume ratio is about 60% hydrogen to about 40% nitrogen while during the summer months, the preferred volume ratio is about 50% hydrogen to about 50% nitrogen.
Although it may be possible to feed the mixture into contact with the catalyst in a number of different ways, it is preferred to introduce the mixture into the heater using the existing fuel gas inlet system.
To this end, a second or preheat valve 38 is provided in accordance with the invention in a separate conduit 40 connected between the main valve 32 and the gas inlet 28 . Thus, during start-up of the catalytic heater, the main valve 32 is kept closed and the preheat valve 38 is opened to allow the hydrogen and nitrogen mixture to flow from a suitable supply, such as a mixing tank 42 , into the plenum chamber 26 and thence through the insulating layer 18 into contact with the catalyst. It should be noted that while only a single inlet valve 28 is shown in the drawing, the gas inlet means may comprise separate or multiple gas inlets for both the starting gas mixture and the fuel gas as will readily occur to those skilled in the art.
To facilitate the preheating method of the invention, there is also provided in accordance with the invention a thermocouple 44 or other temperature sensing device located in proximity to the insulating layer 18 . The temperature of the initial reaction of the hydrogen/nitrogen mix is sensed via the thermocouple 44 and after as little as two minutes, the reaction will have reached a stable temperature. At that point, the hydrogen/nitrogen mix is turned off by closing the preheat valve 38 and opening the main operating valve 32 . This in turn purges the remainder of the hydrogen/nitrogen mix through the catalyst, maintaining the reaction until the main fuel arrives and is subsequently flamelessly oxidized. The main fuel is fed into the heater at a maximum rate for a given heater for about 2 to 5 minutes, ensuring that the reaction is well established.
In order for the preheat method of the invention to work effectively, the gas mixture should be evenly disbursed across the catalyst surface. This is readily achieved by employing a baffling medium such as a metal mesh or screen 46 positioned adjacent to the dispersion plate 22 and the plenum chamber 26 , as disclosed in my U.S. Pat. No. 6,045,355 issued on Apr. 4, 2000, entitled “Gas Catalytic Heaters With Improved Temperature Distribution”, the disclosure of which is incorporated herein by reference. However, it will be understood that catalytic heaters using other methods for uniformly dispersing the fuel gas may work as well, albeit not as efficiently, taking longer for the reaction to spread across the catalyst surface.
It will thus be seen that by using a blend or gas mixture of nitrogen and hydrogen in the volume ratios mentioned herein above effectively controls the richness of the hydrogen and hence the temperature of reaction while creating a gas that is easily distributed through existing manifolds and gas controls for the catalytic system. Moreover, this mix more closely resembles the density properties of natural gas as opposed to those of 99% pure hydrogen gas.
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The invention provides a method of preheating a catalyst in a catalytic heater comprising the steps of preparing a gaseous mixture of hydrogen and nitrogen in a volume ratio of between about 95% hydrogen to about 5% nitrogen and about 5% hydrogen to about 95% nitrogen and dispersing the gaseous mixture into contact with the catalyst for a period of time sufficient to raise the temperature of the catalyst to a level that will promote the flameless oxidation of a fuel gas in the presence of the catalyst.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is a method that is herein described as a Transmedian Storage and Transfer Device (TSTD) that will provide a more useful system for information storage, retrieval, and computation. This is achieved by increasing the speed and storage capacity beyond that provided by existing computers and related systems. To obtain these benefits, the TSTD utilizes a spherical surface for information storage along with a system detector that can be point-like, line-like, or spherical. Further more, multiple spheres can be incorporated into the TSTD thus resulting in a sphere matrix. The present art will improve the current technology by providing unexpected results as it relates to speed, convenience, security and information retrieval. The present art and novel new invention provides a completely new principle of operation for the storage and retrieval of data. In fact this novel new art provides unsuggested combination of old and antiquated technology that does not relate to the present art.
2. Description of the Related Art
The use of different types of storage devices and computers are well known in the art. It is known that the usefulness of a computer system is limited by the speed at witch its operations can be conducted and the amount of information that can be stored within the system. These limitations are the result of existing computer theory, design, and construction. In comparison to the human brain, it is possible for a large volume of information to be stored in various existing systems, however the information cannot be quickly retrieved or acted upon. And although many computer systems can operate quickly, the amount of information processed in those systems is relatively limited. To increase the speed of operation (storage, retrieval, and command execution), and to increase the information storage capacity, a new transmedian storage and transfer device (TSTD) has been designed. This novel and new invention overcomes previous limitations. The speed and storage capacity of this invention will allow for higher machine function. Ultimately, this invention may allow for data correlation and interpretation on levels approaching that of the human brain.
Current computer systems rely primarily upon rotating planer surfaces to effect information storage and retrieval. All of the prior art surfaces and systems are set up on linear and 2 dimensional surfaces and device concepts. The surface area of a flat planar surface is strictly limited to the two dimensional interface between the surface of the storage device (e.g. hard-drive disk, CD (compact disk), etc.) which is usually a limited circular flat surface that provides on average only surface area with the standard CD of approximately 2.5 cm. A small spherical transmedian device holds a multiple increase in surface area versus a flat planar surface. It is known in mathematics that a flat circular surface has a surface area defined by πr 2 and a spherical surface has a surface area defined by 4 πr 2 . This means that a sphere has 4 times the surface area of a flat planar circular surface such as a CD. Spheres also do not have to have a hole in the center of it like a CD or hard drive so that it can be spun at a particular rpm. The spherical device would be a solid device with a smooth or non-smooth surface. These surfaces, which can either be magnetic or optical (disk or disc), rotate about a mostly fixed detector. Inherent limitations arise from the necessary interaction of the detector to the flat rotating surface containing the stored or to be stored information. To overcome these limitations, the TSTD utilizes a spherical surface for information storage. And the system's detector can either be point-like (such as that which is in common use today), or it can be line-like and circle the storage sphere, or it can be spherical in shape itself and surround or be enclosed within the storage sphere in the same manner. The detector can use reflectance in order to detect the data on the surface of the sphere, such that a beam from the detector strikes a particular point on the surface of the sphere and the beam is reflected back to the detector and the data is absorbed, detected, etc., by the detector. Other enhancements to the use of reflectance would be the use of a wide-angle lens attached to the detector or the detector completely encompassing the sphere such that it is completely enclosed. The use of multiple detectors placed on quadrants around the sphere would work and the enhancements such as wide-angle lenses would empower the detectors full coverage of the surface of the sphere. The preferred placement of the detector is adjacent to the outside of the storage sphere however; it can be placed within the sphere. In addition to the single storage sphere and detector system thus far described, more than one sphere and detector can be incorporated into the TSTD depending upon the speed and storage capacity desired for the system. A multiple sphere system (sphere matrix) can be constructed which may allow for even greater system function. Various combinations of storage spheres and detectors are possible. These combinations include multiple detectors per storage sphere, various placement of the detectors within or outside of any given storage sphere or spheres, and the incorporation of multiple detector types (point, line, or sphere) within any system. For example, one TSTD may utilize a storage sphere surrounded by a detector sphere which has one or more detector points operating on its outside. Yet another variation of the TSTD may utilize a single point detector proximally placed between two storage spheres. Many variations are possible with this TSTD invention. Some variations have greater potential than others.
Different attempts at providing an effective storage have been developed using the same planar surface approach. No prior are found or ever will be found can described the present arts novelty. However for discussion purposes the following systems are in the same field but have no relative bearing on the present art. U.S. Pats. No. 6,449,697 is a patent for pre staging data into cache in preparations for data transfer operations and has nothing to do with the present art and does not teach a sphere for the storage of data, a magnetic filed for use, a spherical detector system that encompasses the data sphere, etc. This prior art has nothing to do with the present art. U.S. Pat. No. 6,449,688 is a device for the process of transferring streams of data between multiple storage units and multiple applications in a scalable and reliable manner. This again, uses old antiquated linear technology and thought, and does not teach or even elude to the novelty of the present art, this art does not teach a sphere for the storage of data, a magnetic filed for use, a spherical detector system that encompasses the data sphere, etc. U.S. Pat. No. 6,449,689 does teach the storing of compressed data on a hard disk drive, but again, this antiquated technology and thought does not have anything to do with the advancement in the art the present device does. In addition this art does not teach a sphere for the storage of data, a magnetic filed for use, a spherical detector system that encompasses the data sphere, etc.
While the prior art provides methods for the storage of data, its maximum capacity for storage on a DVD is 8.5 MB of data. On a spherical surface it would be 4 times that amount as a minimum with a smooth surface (in the neighborhood of 34 MB). This is purely for illustration purposes only. The technology (preset art) is so new that it brings about a basic paradigm shift in thought with regards to the storage of data. All of the prior art suffer from the limited one to two dimensional surface areas when dealing with a flat circular planar surface, there are additional drawbacks but need not be mentioned now. These are just some, but not all, of the limitations of the prior art.
SUMMARY OF THE INVENTION
The present invention is designed to advance the art of data storage and retrieval past the prior arts drawbacks and provide a marked in improvement in the art. The present art requires minimal number of parts, increases speed and is cost effective. Another object of the present invention is to provide a method that allows for an easily adaptable method of use and is fully enabled.
The primary object of the present invention is to provide a more useful system for information storage, retrieval, and computation. This is achieved by increasing the speed and storage capacity beyond that provided by current computer systems while at the same time maintaining a device size that is generally consistent with the common use of existing computers. A secondary object of the present invention is to provide a system that could or may be powerful enough to allow for higher levels of information correlation and interpretation.
The act of storing information on the TSTD storage sphere can be achieved magnetically, optically, or by some other means. The sphere can float within a magnetic field, or other repulsion or attraction median, or within a fluid or liquid, or be held or supported by connective mounts that allow for up to a full three axes motion of the sphere itself, or it can be held or supported by any combination of these. The TSTD detector can float within a magnetic field, or other repulsion or attraction median, or within a fluid or liquid, or be held or supported by connective mounts that allow for up to a full three axes motion of the detector itself, or it can be held or supported by any combination of these. For each storage sphere or detector that may be added to or comprise the system (a sphere matrix), they also can float within a magnetic field, or other repulsion or attraction median, or within a fluid or liquid, or be held or supported by connective mounts that allow for up to a full three axes motion of the items themselves, or they can be held or supported by any combination of these. As previously explained in exacting detail the current computer systems rely primarily upon rotating planer surfaces to effect information storage and retrieval. All of the prior art surfaces and systems are set up on linear and 2 dimensional surfaces and devices concept. The surface area of a flat planar surface is strictly limited to the two dimensional interface between the surface of the storage device (e.g. hard-drive disk, CD (compact disk), etc.) which is usually a limited circular flat surface that provides on average only surface area with the standard CD of approximately 2.5 cm. A small spherical transmedian device holds a multiple increase in surface area versus a flat planar surface. It is known in mathematics that a flat circular surface has a surface area defined by πr 2 . A sphere has a surface area defined by 4 πr 2 . Thus a sphere represents 4 times the surface area of a flat planar circular surface such as a CD. For starters spheres do not have to have a hole in the center of it like a CD or hard drive so that it can be spun at a particular rpm. The spherical device would be a solid device with a smooth or non-smooth surface. These surfaces, which can either be magnetic or optical (disk or disc), rotate about a mostly fixed detector. Inherent limitations arise from the necessary interaction of the detector to the flat rotating surface containing the stored or to be stored information. To overcome these limitations, the TSTD utilizes a spherical surface for information storage. And the system's detector can either be point-like (such as that which is in common use today), or it can be line-like and circle the storage sphere, or it can be spherical in shape itself and surround or be enclosed within the storage sphere in the same manner. The detector can use reflectance in order to detect the data on the surface of the sphere, such that a beam from the detector strikes a particular point on the surface of the sphere and the beam is reflected back to the detector and the data is absorbed, detected, etc., by the detector. Other enhancements to the use of reflectance would be the use of a wide-angle lens attached to the detector or the detector completely encompassing the sphere such that it is completely enclosed. The use of multiple detectors placed on quadrants around the sphere would work and the enhancements such as wide-angle lenses would empower the detectors full coverage of the surface of the sphere. The preferred placement of the detector is adjacent to the outside of the storage sphere however; it can be placed within the sphere. In addition to the single storage sphere and detector system thus far described, more than one sphere and detector can be incorporated into the TSTD depending upon the speed and storage capacity desired for the system. A multiple sphere system (sphere matrix) can be constructed which may allow for even greater system function. Various combinations of storage spheres and detectors are possible. These combinations include multiple detectors per storage sphere, various placement of the detectors within or outside of any given storage sphere or spheres, and the incorporation of multiple detector types (point, line, or sphere) within any system. For example, one TSTD may utilize a storage sphere surrounded by a detector sphere which has one or more detector points operating on its outside. Yet another variation of the TSTD may utilize a single point detector proximally placed between two storage spheres. Many variations are possible with this TSTD invention. Some variations have greater potential than others. Depending upon the TSTD detector desired for use (point, line, reflectance, multiple or spherical), the storage and retrieval of information (the transfer of data) from the TSTD could be from any direction of the device at any point, or from all points and orientations simultaneously. The ability to acquire data from a much larger pool is an advancement of an unrecognized solution to a problem such as limited data storage and retrieval. And this transfer can occur sequentially or simultaneously. The only computer that can currently come anywhere near this ability is the human brain. The present art will give the ability to computer, robots, androids and the like to achieve the unthinkable, process information at the speed of the human brain.
The benefits provided by the TSTD invention described thus far include increased operational speed and increased storage capacity. The larger surface area of the sphere affords the improved storage capacity over that of the common planner disk. The improved speed is afforded by the ease that data storage and retrieval can be conducted due to the interaction of the detector with the storage sphere. More specifically, it is the ability of the detector and storage sphere to move in a greater relative motion to one another and to cover a greater surface area in less time that results in the increased operating speed.
To affect a relative motion or non-motion of the detector to the sphere can be accomplished by electrical, magnetic, or mechanical means. For example, the data sphere (in this example metallic, but can be made out of any suitable material that can be used to store data) is surrounded by a metal (magnetic) cover that is controlled by electricity (e.g. that when manipulated can determine the amount and position of the data sphere relative to the outer detector and the data sphere is controlled by an electrical current applied to the outer shell of the outer (detector) sphere. This would allow the manipulation of the sphere to orient it to any particular point relative to the inside surface of the detector (outer shell). The detector in this example could be made up of 4 individual detectors (but could be as many as one, thousands or more) that can detect reflectance, light, etc., that are placed perpendicular to each other in such a manner to give the detector(s) full coverage of the data sphere using fish-eye or some other curved lens. In addition the detector(s) can use laser, diodes, fiber optics or some other mode for the transmittal of data in the form of electrical pulses that were converted from light that is reflected or otherwise from light energy to electrical form the surface of the data sphere within the transmedian device.
The present example of the invention provides a method of data storage and or retrieval that allows the use of a single data sphere inside of a magnetic spherical detector that encompasses the internal data sphere as defined above, and the method being characterized by the following steps:
a) enclosing a data sphere with an external detector sphere; b) the data sphere is made up of a material that stores data and can be manipulated within a magnetic field; c) the external sphere detector sphere is made up of a material that can exert a magnetic field with the use of electricity or some other form of energy; d) the detector has 4 detectors (in this example light detectors) that are perpendicular to each other;
Other aspects and advantages of the present invention appear more clearly from reading the following detailed description of the preferred embodiment of the invention, given by way of example and made with reference to the accompanying drawings. Such as the determination of the shape and orientation of the spheres to each other, etc. A thorough search of the literature reveals no relative art resembling this technology; therefore, this invention is clearly a novel in creation, and is not obvious to anyone skilled in the art, there are certain aspects of the present art that can be found in the prior art but no prior art has advanced the art of data storage/retrieval as much as the present art. This art solves an unrecognized problem that was never before even recognized. Specifically this novel art allows for the user the unexpected results of increasing memory storage and retrieval exponentially. This was never conceived until the present art and advances the art significantly. In fact the prior art as cited teach away from the present art in that it teaches the use of flat planar surfaced for the storage of data, the use of single detectors, circular surfaces not spherical, etc.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects, features and advantages of the invention will become obvious from the following detailed description of the invention when taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a plan view of a storage (data) sphere using a point detector according to the present invention;
FIG. 2A is a perspective view of a storage (data) sphere using a line detector according to the present invention;
FIG. 2B is a top view of the storage (data) sphere of FIG. 2A using a line detector;
FIG. 3 is a plan view of a storage (data) sphere using a sphere detector according to the present invention; and
FIG. 4 is a plan view of two storage (data) spheres relative to two detectors.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will now be described more fully with reference to the accompanying drawings, in which the preferred embodiments of the present art invention are shown. It is understood from the embodiments that a person skilled in the art may make variations and modifications without departing from the spirit and scope of the invention. Such as changing the size or shape of the sphere from a pure round sphere to an oblong sphere, etc., the use of one or more detectors, the surface of the device, the materials that the device is made from, etc.
Referring now to the drawings and in particular FIG. 1 is a plan view of one embodiment of the storage (data) sphere 1 that is used for storage and retrieval of data and the detector (point) 3 . FIG. 1 shows a single storage sphere 1 and a single point-like detector 3 (one that is in common use today). Data transfer to and from the storage sphere 1 occurs at the “point” of the detector 3 . FIG. 2A shows a single storage sphere 1 and a single line-like detector 3 . Data transfer to and from the storage sphere 1 can occur along the entire length of the “line” of the detector 3 . In FIG. 2B a top view of the storage (data) sphere of FIG. 2A using a line detector 3 is clearly illustrated. FIG. 3 is a top view of a storage (data) sphere 1 using a pulse detector 3 . The dashed lines 9 as illustrative of this type of detector 3 are further illustrated by the dashed lines 9 that surround the sphere 1 . The dashed lines 9 represent the pulsing of the pulse detector 3 .
Therefore, FIG. 3 shows a single storage sphere 1 and a single sphere-like detector 3 . Data transfer to and from the storage sphere 1 can occur along the entire surface of the sphere of the detector 3 . FIG. 4 is a plan view of two storage spheres 1 relative to the detectors 3 . FIG. 4 illustrates an example of TSTD comprised of two point detectors 3 that are positioned between two storage spheres 1 . An embodiment of the current invention can further include detectors 3 , power supply line (not shown) for the magnetic field which can be filled with fluid or empty or under a vacuum or pressure, detector lens (curved) (not shown) and detector connection line (not shown). It is contemplated that the detectors 3 can provide complete coverage of the whole sphere 1 . Therefore the device provides a full coverage for all of the information available on the surface of the sphere 3 . An embodiment can further include the power supply line (electrical current for example) (not shown) for the magnetic field which can be filled with fluid or other substance or empty or under a vacuum or pressure, the detector lens (curved) (not shown), and the detector connection line (not shown). To affect a relative motion or non-motion of the detector 3 to the sphere 1 can be accomplished by electrical, magnetic, or mechanical means. For example, the data sphere 1 (in this example metallic, but can be made out of any suitable material that can be used to store data) is surrounded by a metal (magnetic) cover 3 (detector) that is controlled by electricity (e.g. that when manipulated can determine the amount and position of the data sphere 1 relative to the outer detector 3 and the data sphere 1 is controlled by an electrical current 6 applies to the outer shell of the outer (detector) sphere 3 . This would allow the manipulation of the sphere 1 to orient it to any particular point relative to the inside surface of the detector(s) (outer shell). The detector 3 in this example could be made up of 4 individual detectors 3 (but could be as many as one, thousands or more) that can detect reflectance, light, etc., that are placed perpendicular to each other in such a manner to give the detector(s) 3 full coverage of the data sphere 1 using fish-eye 5 or some other curved lens 5 . In addition the detector(s) 3 can use laser, diodes, fiber optics or some other mode for the transmittal of data in the form of electrical pulses that were converted from light that is reflected or otherwise from light energy to electrical form the surface of the data sphere 1 within the transmedian device.
The present example of the invention provides a method of data storage and or retrieval that allows the use of a single data sphere inside of a magnetic spherical detector that encompasses the internal data sphere as defined above, and the method being characterized by the following steps:
e) enclosing a data sphere with an external detector sphere; f) the data sphere is made up of a material that stores data and can be manipulated within a magnetic field; g) the external sphere detector sphere is made up of a material that can exert a magnetic field with the use of electricity or some other form of energy; h) the detector has 4 detectors (in this example light detectors) that are perpendicular to each other;
The simplicity and novelty of the invention is unmatched in the art. This device could be easily manipulated to increase the data and storage capacity of any system. This invention is going to save the mankind, the world, computer industry and users billions to trillions of dollars in by increasing the storage and retrieval of data, increasing the speed at which data can be accessed, and improving technology and life as a minimum.
To further explain in a brief and concise way the present art is a method for data storage and retrieval using a sphere and detector wherein the following is required;
a. a sphere with an external detector; b. the above mentioned sphere is made up of a material that stores data and can be manipulated within a magnetic field or by other mechanical or electrical means; c. the detector can be a line, pulse, point, spherical, or multiple that can convert light or other energy to electrical pulses that can be interpreted by a computer or other device as data or code.
The invention has been described in detail with particular reference to a preferred embodiment and the operation thereof and it is understood that variations, modifications, and substitution of equivalent means can be effected and still remain within the spirit and scope of the invention. And all such modifications and variations are to be included within the scope of the invention as defined in the appended claims.
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There is herein described a Transmedian Storage and Transfer Device (TSTD) that will provide a more useful system for information storage, retrieval, and computation. This is achieved by increasing the speed and storage capacity beyond that provided by existing computers and related systems. To obtain these benefits, the TSTD utilizes a spherical surface for information storage along with a system detector that can be point-like, line-like, or spherical. Further more, multiple spheres can be incorporated into the TSTD thus resulting in a sphere matrix.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. patent application Ser. No. 11/296,555, filed Dec. 7, 2005 and entitled Secure Pin Entry Device for Mobile Phones, which is hereby incorporated by reference in its entirety for all purposes, which is a continution-in-part application to U.S. patent application Ser. No. 11/226,823, filed Sep. 14, 2005, which claims priority to U.S. Patent Application Ser. No. 60/611,455, filed Sep. 20, 2004, each of which is incorporated by reference.
BACKGROUND AND SUMMARY
[0002] Secure PEDs are used in connection with Point of Sale (POS) devices, ATMS, or computers for performing secure PIN entry requiring electronic transactions. These transactions are typically payment transactions or secure information exchange. The function of the PEDs is to prevent third parties from tampering with the above mentioned transaction devices in an attempt to steal the PIN from consumers who use them. PEDs must go through a certification process administered by local or global certification authorities. In order for the PEDs to pass the certification process they must meet certain security standards including secure storage of public/private keys provided from acquiring banks and processors for encryption and authentication. The PEDs must also have the ability to deter tampering with the device, i.e., be “Tamper Resistant”, “Tamper Evident”, and “Tamper Responsive”. A device is “Tamper Resistant” if it prevents easy access to the PED and does not allow third parties to intercept the key strokes and steal the customer's PINs. A device is “Tamper Evident” if it becomes very apparent to the user when the device has been tampered with. A device is “Tamper Responsive” if in case someone attempts to tamper with the PED, the secure data of the PED that are used for the transactions get automatically erased from the memory thereby making the device useless for secure transactions. In one example, the certification requirements for the PEDs are described in the Payment Card Industry (PCI) PED specification, published on the Visa International website http://international.visa.com/fb/vendors/pin/reference.jsp. A secure PED must be certified by the appropriate authorities approved by Visa and MasterCard and once it has passed certification according to specifications and test, the device name is published as “certified.” A secure PED may be a stand-alone device or it may be integrated with the transaction device, as is the case for POS and ATM. However, most PEDs have a rectangular, box-like form and are usually large compared to typical mobile phone devices.
[0003] A mobile phone device is defined by its functionality and “form factor”. The main function of a mobile phone is to make phone calls in a mobile environment. Accordingly, a mobile phone or phone module includes hardware and software components that provide voice and data functionality over a wireless network. Today there are simple low cost mobile phones that perform just phone calls. There are also more expensive mobile phones that come with different ancillary features like digital cameras, PDA features, SMS, MMS, music, games, email, video streaming, among others. However, the core function of a mobile phone is simply its ability to make phone calls and if this function is removed the device is not a mobile phone anymore. Conversely if there is phone capability and any of the other ancillary features are removed, the device would still be a mobile phone. However, having the ability to make a phone calls in mobile environments alone does not make a device a “mobile phone”.
[0004] Another important characteristic that defines a mobile phone is its “form factor”, i.e., the look and feel of the device. Mobile phones come in several different physical styles or “form factors”. While manufacturers are continually coming up with new types of designs, there are several common categories used to describe form factors of mobile phones:
i) Bar: (candy-bar or block) This is the most basic style. The entire phone is one solid monolith, with no moving parts aside from the buttons and possibly antenna. ii) Clamshell: (folder) This type of phone consists of two halves, connected by a hinge. The phone folds closed when not in use. The top half usually contains the speaker, and the display or battery, with the bottom half containing the keypad and remaining components Most clamshell phones have a feature called Active Flip, which means that calls can be answered and ended by simply opening and closing the phone. iii) Flip: This type of phone is a cross between the Bar and Clamshell types. Most of the components of the phone are in one part, but a thin “flip” part covers the keypad and/or display when not in use. The flip may be all plastic, or it may contain one or two minor components such as a speaker or secondary keys. Most flip phones also feature Active Flip, as described above. iv) Slide: This type is usually designed similarly to a clamshell, with a large main display and speaker in one half, and the keypad and battery in the other half. But the two halves slide open instead of using a hinge. Slide designs allow the main display to be seen when closed, and are generally easier to open and close one-handed.
[0009] All these mobile phone designs are recognized as mobile phones and have the following common features. They are small enough so as to fit in a person's hand. Typical dimensions are in the range of 2-8 inches length and 1.5-3 inches width. They have a shape such that one can put the mobile phone up to his ear to listen and at the same time close to his mouth to talk. They have low weight. The weight is in the range of 4-9 ounces. If the device is larger or smaller it acquires another recognizable form factor. For example, a PC or a laptop can perform mobile phone functions when one plugs a radio module into it, but it still has the form factor of a PC or a laptop. The same is true with Tablet PC, or even a POS device that can perform mobile phone functions like a Lipman8000 mobile POS which can also dial a phone call, nonetheless it is still has a POS form factor and not a mobile phone form factor. Today's convergence of PDAs and mobile phones is still considered by the general public as having the form factor of a mobile phone because of size, shape and weight. These PDA-mobile phone devices are sized to fit into one's hand and one can hold them up close to his ears to listen and at the same time close to his mouth to talk in a way similar to how the average person would consider using a mobile phone. A larger size or a smaller size than that would start turning the mobile phone into a different form factor. For example one day when mobile phone capabilities are inserted into a wristwatch, that form factor will no longer be a mobile phone form factor, but it would be the form factor of a wristwatch. Thus form factor is important for defining a mobile phone.
[0010] Mobile phones have been combined with card readers to provide a new range of POS type terminals for conducting financial services transactions. While there are several card readers available today for mobile phones, offered by Semtek, Symbol, Apriva, none of these devices meet the PED security certification requirements. Most of these prior art devices are focused on the credit card market and are not designed for conducting debit card transaction where PIN entry is required. The keypads on the mobile phones are not secure and have not been approved or certified by major financial institutions. Accordingly, the current mobile phonecard reader combination devices do not meet the security requirements and cannot be certified for PIN entry requiring transactions.
[0011] Prior art POS devices with a certified PED have used a phone as an external modem for providing communications, similar to the way personal computers use a phone as an external modem for providing communications. However this is not a certified PED “integrated” with the phone as one device, but rather a POS that links to a phone. All these prior art POS devices function as standalone POS that link to other communication mediums, such as cable modems, DSL modems, or other dialup terminals, independent of the phone and thus are not considered to be an integrated unit with the phone. Furthermore, these devices do not have the form factor of a mobile phone. There are also prior art POS with a certified PED that use a wireless modem. However, these are wireless POS devices, and not a wireless mobile phone-POS with an “integrated” secure PED. Also, these devices do not have the form factor of a mobile device. Some of the wireless POS allow one to plug a separate microphone headset to dial a phone call, but it is still a POS and has the form factor of a POS and one would not consider it a mobile phone.
[0012] Accordingly, there is a need for a secure PED module that is certified by the various financial institutions and can be integrated with a mobile phone as one device to provide the small and convenient form factor and functionality of a mobile phone, while having the capabilities of a secure PED to enable POS various payment transactions including debit, and EMV.
[0013] In general, in one aspect this invention features a secure mobile phone-point of sale (mobile phone-POS) system for conducting secure PIN entry requiring electronic transactions. The secure mobile phone-POS includes a mobile phone, a secure PED and software and hardware components for processing the secure PIN entry requiring electronic transactions. The secure PED includes a keypad, a screen display and security components effecting the keypad and the screen display to meet certification requirements of a certification institution for conducting the secure PIN entry requiring transactions. The secure PED is integrated with the mobile phone and the system has the functionality of both the mobile phone and the secure PED.
[0014] Implementations of this aspect of the invention include the following. The secure mobile phone-POS system has a mobile phone form factor. The mobile phone form factor may be bar type, clamshell, flip or slide. The mobile phone-POS system has a length in the range of 2-8 inches, width in the range of 1.5-3 inches and weight in the range of 5-10 ounces. The mobile phone includes a serial interface port and the secure PED is integrated with the mobile phone via the serial interface port. The mobile phone includes a Printed Circuit Board Assembly (PCBA) and the secure PED is integrated directly with the mobile phone's PCBA. The mobile phone includes a mobile phone PCBA and the secure PED comprises a PED PCBA and the mobile phone PCBA is integrated with the PED PCBA via a connector. The secure PED includes a Printed Circuit Board Assembly (PCBA) and the mobile phone includes a radio communication module integrated directly onto the secure PED's PCBA. The mobile phone further includes an antenna, a speaker, and a microphone, and the antenna, the speaker and the microphone are integrated directly onto the secure PED's PCBA. The mobile phone-POS system further includes a PCBA and the mobile phone and the secure PED are integrated directly onto the mobile phone-POS PCBA. The mobile phone includes a
[0015] Subscriber Identification Module (SIM) slot and the secure PED is integrated with the mobile phone via the SIM slot. The certification requirements of a certification institution may be the Payment Card Industry (PCI) PED specification, Europay MasterCard Visa (EMV) Level 1 and level 2 standard compliance, Bank Card testing Center of China (BCTC), Zentraler Kreditausschuss (ZKA) and Interac. The security components include a microprocessor, RAM, SAM slot for receiving a SAM module, smart card reader/writer, screen display, keypad, battery, flash memory, erasable memory, and detector switches, serial port, magnetic card reader, hardware id, real time clock, Bluetooth, Infrared port, SIM slot for connecting to the mobile phone or SIM slot for receiving a SIM card. The software components include protocol (TACP). The hardware components include microprocessor, RAM, SIM slot, SIM card, SAM card, SAM slot, smart card reader/writer, screen display, keypad, battery, flash memory, erasable memory, serial port, magnetic card reader, real time clock, Bluetooth, Infrared port, IrDA and printer. The software and hardware components for processing the secure PIN entry requiring electronic transactions may be included in the secure PED or the mobile phone. The mobile phone may also include a phone screen display and a phone keypad that do not meet certification requirements of a certification institution for conducting the secure PIN entry requiring transactions.
[0016] In general in another aspect the invention features a secure mobile phone-POS system for conducting secure PIN entry requiring electronic transactions, including a mobile phone, a secure PED and software and hardware components for processing the secure PIN entry requiring electronic transactions. The mobile phone includes a keypad, a screen display, a Printed Circuit BoardAssembly (PCBA) and software and hardware components for processing the secure PIN entry requiring electronic transactions. The secure PED includes security components effecting the keypad and the screen display of the mobile phone to meet certification requirements of a certification institution for conducting the secure PIN entry requiring transactions. The secure PED is integrated directly with the mobile phone's PCBA. The secure mobile phone-POS has the functionality of both the mobile phone and the secure PED and a mobile form factor
[0017] In general in another aspect the invention features a method for conducting secure PIN entry requiring electronic transactions, comprising the following steps. First providing a mobile phone. Next, providing a secure PED that includes a keypad, a screen display and security components effecting the keypad and the screen display to meet certification requirements of a certification institution for conducting the secure PIN entry requiring transactions. Next, providing software and hardware components for processing the secure PIN entry requiring electronic transactions. Finally, integrating the secure PED with the mobile phone to form one unit.
[0018] In general in another aspect the invention features a pin entry device including a keypad, a screen display and security components effecting the keypad and the screen display to meet certification requirements of a certification institution for entering and displaying security sensitive information, respectively. The pin entry device is integrated with a nonsecure mobile phone thereby upgrading the mobile phone's non-secure screen display and keypad with the security components.
[0019] Among the advantages of this invention may be one or more of the following. The secure PED is a self-sufficient payment enabling module. It is capable of accepting entry and displaying information in a way that satisfies the payment card industry security standards. The secure PED performs electronic payment transactions by interacting with banking cards and payment processors. Depending on the level of integration the secure PED may not have payment processing functionality implemented by the device itself. The secure PED is responsible for the secure PIN entry and display functionality and the mobile phone is responsible for sending the data for processing of the transaction by a host. The secure PED with or without payment processing capability conforms to security standards imposed by the payment industry. These standards are the same standards that are applicable for networked POS (Point Of Sale) Terminals commonly used in the industry.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 shows a schematic diagram of a dual keypad mobile phone-POS system that includes a secure PED integrated with the mobile phone via a SIM slot;
[0021] FIG. 2 shows a schematic diagram of a dual keypad mobile phone-POS system that includes a secure PED integrated with the mobile phone via a serial port;
[0022] FIG. 3 shows a schematic diagram of a dual keypad mobile phone-POS system that includes a secure PED integrated directly with the mobile phone's PCBA;
[0023] FIG. 4 shows a schematic diagram of a single keypad mobile phone-POS system that includes a secure PED integrated directly with the mobile phone's PCBA;
[0024] FIG. 5 depicts front, side and toy views of two bar type single keypad/display mobile phone-POS system;
[0025] FIG. 6 shows a front view of a bar type dual keypad/display mobile phone-POS system;
[0026] FIG. 7 shows a back view of a bar type dual keypad/display mobile phone-POS system;
[0027] FIG. 8 shows a top view of a bar type dual keypad/display mobile phone-POS system; and
[0028] FIG. 9 shows a front view of a bar type dual keypad/display mobile phone-POS system connecting remotely to a printer.
DETAILED DESCRIPTION
[0029] Referring to FIG. 1 , a secure PED 90 includes a main microprocessor 102 , Random Access Memory (RAM) 104 , erasable memory 105 , persistent flash memory 106 , a Subscriber Identification Module (SIM) slots 108 , 109 , Secure Authentication Module (SAM) slot 110 , smart card reader/writer 112 , magnetic stripe reader 114 , Infrared Data Association (IrDA) port 122 , Serial port 124 , Liquid Crystal Display (LCD) screen 116 , keypad 120 , life-time battery 118 , real time clock 119 , and detector switches. The main micro-processor 102 controls all other components of the device and runs all operational environment and application programs. The RAM 104 and the persistent flash memory 106 store program and data. SIM slot 108 provides the ability to connect to the SIM card of a GSM enabled Mobile Phone 200 . SIM slot 109 provides the ability to connect another phone SIM card. SAM slot 110 provides the ability to insert a Secure Authentication Module that is used for the authentication purpose of the payment application. The smart card reader/writer 112 and the magnetic stripe reader 114 are used to read and write smart cards and to read magnetic stripe cards, respectively. These type of card interactions are needed for performing payment transactions utilizing banking payment cards. The IrDA 122 and/or the serial port 124 provide the ability to communicate with an external printer or other peripherals. The LCD screen 116 and the key/PIN pad 120 provide the ability to display information on the screen and to input information by pressing keys. The lifetime battery 118 provides power to the components that require independent and permanent power supply such as the real time clock 119 and the erasable memory 105 . The erasable memory 105 contains sensitive data that will be automatically erased by removing the power supply. Usually this memory is used to store such highly sensitive data as encryption keys. The detector switches 117 detect any device tampering attempt and effectively cut-off power supply from the erasable memory.
[0030] There are several ways of integrating the secure PED 90 to a mobile phone 200 . Referring to FIG. 1 , the secure PED 90 is integrated with a SIM enabled mobile phone 200 by connecting the phone's SIM card 206 to the SIM slot 108 . This integration method preserves all of the secure PED's components that are described above. In this case the integrated mobile phone-POS device has two screens and two keypads. The mobile phone screen 202 and keypad 204 do not have the ability to securely enter and display sensitive information. The secure PED screen 116 and keypad 120 provide the ability to securely enter and display sensitive information. The integration between the mobile phone 200 and the secure PED is done using GSM standard “SIM Card Toolkit” that allows the PED to interact with the phone for the purpose of performing payment transaction.
[0031] Referring to FIG. 2 , the PED 90 is integrated with the mobile phone 200 via the serial port 150 . This integration method preserves all of the secure PED' s components that are described above except of the SIM slot 108 . In this case the integrated mobile phone-POS device 100 has two screens and two keypads. One set of screen 202 and a corresponding keypad 204 comes from the mobile phone 200 and this set does not have the ability to securely enter and display sensitive information. The other set of the screen 116 and keypad 120 comes from the PED and this set has the ability to securely enter and display sensitive information. The integration between the mobile phone and the PED is done using mobile phone standardAT-command set that allows the PED to interact with the mobile phone for the purpose of transmitting payment transaction data to and from the transaction processing center.
[0032] Referring to FIG. 3 , the PED 90 is integrated directly with the mobile phone's PCBA 220 . This integration method preserves all of the device components listed above with the exception of the SIM slot 108 . In this case the secure PED's components are directly placed in the circuitry of the mobile phone. The mobile phone's circuitry has to be modified to accommodate additional components that provide the PED functionality. The mobile phone's main microprocessor 160 controls all other components of the device and runs all operational environment and application programs. The mobile phone's RAM 162 and persistent flash memory 164 store programs and data. The secure PED's microprocessor 102 , RAM 104 , flash memory 106 , IrDA 122 , and serial ports 150 become optional components that may or may not be present in the integrated mobile phone circuitry. Such integration may preserve the secure PED's screen 116 and keypad 120 in the integrated circuitry (shown in FIG. 3 ) or alternatively may upgrade the mobile phone's screen and pad with the security features from the PED (shown in FIG. 4 ).
[0033] Referring to FIG. 4 , the PED 90 is integrated with the mobile phone's PCBA 220 . This integration method preserves all of the device components listed above with the exception of the SIM slot 108 , LCD screen 116 , and key/PIN pad 120 . The secure PED's microprocessor 102 , RAM 104 , flash memory 106 , IrDA 122 , serial ports 124 become optional components that may or may not present in the integrated mobile phone circuitry. In this case the mobile phone-POS system 100 has only one screen 202 and one keypad 204 that are inherited from the phone 200 . This inherited screen 202 and keypad 204 are protected by the security components of the PED device. In this configuration, the mobile phone can be based on traditional mobile phone PCBA by mobile manufacturers, or it can be based on mobile phone module/radio module, which contains mobile phone capabilities integrated with the PED device and processor.
[0034] Examples of integrated mobile phone-POS systems 100 are shown in FIG. 5-FIG . 9 . Referring to FIG. 5 , each of the two embodiments 100 a, 110 b of single keypad/display mobile phone-POS systems includes a keypad and a display and has the form factor of a bar type mobile phone. They have the functionality of a regular mobile phone, i.e., they perform phone calls in a mobile environment and they are certified and function as secure PEDs. Typical dimensions of these integrated mobile phone-POS systems are in the range of 2-8 inches length and 1.5-3 inches width. The weight of these devices is in the range of 5-10 ounces. Referring to FIG. 6 the dual keypad/display mobile phone-POS device 100 includes a first keypad 204 and a first display 202 on the front side of the mobile phone-POS device. The mobile phone-POS device 100 of FIG. 6 also includes a second keypad 120 and a second display 116 on the back side of the mobile phone-POS device, as shown in FIG. 7 . The mobile phone-POS device 100 of FIG. 6 also includes an IrDA port 122 , shown in FIG. 8 , for connecting to an external printer 250 , shown in FIG. 9 . Other types of mobile phone form factors include the clamshell, the flip and the slide. All of these forms allow one to put the mobile phone up to his ear to listen and at the same time close to his mouth to talk.
[0035] The integrated mobile phone-POS system 100 includes all the hardware components and software components that are required to process electronic payment transactions for banking cards. In one example these software components include a secure transaction application and a transaction application commanding protocol (TACP), described in U.S. patent application Ser. No. 11/226,823, filed on Sep. 14, 2005, and entitled “SYSTEM AND METHOD FOR A SECURE TRANSACTION MODULE” the contents of which are expressly incorporated herein by reference. Only external power supply and communication channel are needed to successfully authorize transaction with the card issuing institution. Depending on the level of integration the PED may not have payment processing functionality implemented by the device itself. In such cases payment processing functionality may be performed by the mobile phone. However, the PED is still responsible for the secure PIN entry and display functionality. The PED with or without payment processing capability conforms to security standards imposed by the payment industry.
[0036] The secure PED of this invention is certified by international and national authorities and institutions. All hardware and software components of the secure PED as well as the PCBA circuitry and packaging are implemented in accordance with the standards that are required for certification. Certification has been obtained by Payment Card Industry (PCI), Europay MasterCard VISA (EMV) and Bank Card Testing Center of China (BCTC) according to PCI PIN Entry Device specification, Europay MasterCardVISA Level 1 and Level 2 standard compliance (EMV Smart Card processing compliance), and BCTC specification, respectively. Certification has also been obtained by the Zentraler Kreditausschuss (ZKA) and Interac.
[0037] Several embodiments of the present invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
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A secure mobile phone-point of sale (POS) system includes a mobile phone integrated with a secure PED module. The secure PED module is integrated with the mobile phone via the phone's serial port or directly to the phone's Printed Circuit Board Assembly (PCBA). The secure PED module conforms to security standards imposed by the payment card industry. The secure mobile phone-POS system has the functionality of both the secure PED and the mobile phone and the look and feel of the mobile phone.
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BACKGROUND OF THE INVENTION
The present invention relates to a device for resiliently retaining the end portion of a decorative trim molding onto an automobile body panel and more particularly, a clip for retaining the end of a molding adjacent an automobile body panel which allows lateral movement of the molding away from the panel, and returns the molding to its original position.
In modern automobile construction, it is common practice to provide bumper arrangements, both in the front and rear of the automobile which blend into the body structure and give the appearance of a unitary structure at the points where the bumpers meet the adjacent panels of the vehicle. In order to accomplish this, automobile designers have aligned the decorative molding, which is attached to the body panels with a similar decorative molding on the bumper, thus giving the appearance of a unitary structure at the point where the bumper and the panel merge to form the body of the vehicle.
In recent years, automobile makers have turned to resiliently supporting the bumper on the vehicle in order to meet certain safety requirements and standards. In general, the bumper arrangement now provided on an automobile includes a support for the bumper which allows the bumper to move inwardly relative to the automobile body on impact. Automobile manufacturers are, therefore, forced to substitute resilient material, such as plastic, between the bumper and body panels in place of sheet metal, such that the body lines at the intersection of the bumper with the body panel still retain a pleasing appearance, yet do not buckle when the bumper is moved inwardly toward the body on impact.
However, so far as trim mold is concerned, heretofore, it has been necessary to end the trim molding at the end of the metal panels on the vehicle body and omit any trim portion overlying the plastic or resilient material which bridges the gap between the vehicle bumper, and the metal panel of the vehicle body.
It is, therefore, the object of the present invention to provide a device which is effective to allow the trim molding of a vehicle body to be extended to abutting relation with a similar trim molding on a vehicle bumper assembly.
It is a further object of the invention to provide a novel device for resiliently retaining an end portion of a molding onto an automobile body panel which allows the end portion of the molding member to be moved outwardly on bumper impact, from the body to allow the aligned molding on the bumper to move past it and which is effective to retain the molding to the aligned position on the body after a plurality of such movements.
SUMMARY OF THE INVENTION
The above objects and other objects which will become apparent as the description proceeds, are accomplished by providing for use with an automobile body and bumper assembly wherein relative movement takes place between a body panel and bumper, each of which carries a portion of an aligned molding thereon, a resilient member for receiving a molding on the body panel in engagement therewith near the molding end adjacent the aligned molding portion on the bumper and means affixing the resilient member to the automobile body panel. Movement of the bumper relative to the body is effective to cause the body molding to move away from the body by causing flexure of the member. The device for resiliently retaining the end portion of the molding onto the panel generally comprises a body portion having a width less than that of the molding and a length extending along a portion of the molding length and the means for engaging the body portion onto the molding with the device disposed between the molding and the panel. The device further comprises a resilient tongue affixed to the body portion near the end portion of the molding and extending along the portion of the molding length and means disposed near the distal end of the tongue for affixing the tongue to the panel.
BRIEF DESCRIPTION OF THE DRAWING
For a more complete understanding of the invention, reference should be made to the following description taken in conjunction with the accompanying drawing wherein:
FIG. 1 is a fragmentary perspective view having portions in section showing an automobile body wherein the bumper is movable relative to the body, and in which the present invention is employed;
FIG. 2 is a fragmentary perspective view similar to FIG. 1 showing the automobile body and bumper during impact caused by collision of the bumper with an object;
FIG. 3 is an exploded perspective view showing elements of the invention;
FIG. 4 is a plan view showing details of the structure of FIG. 3;
FIG. 5 is an exploded perspective view showing the structure of FIGS. 3 and 4 employed in conjunction with a molding and automobile panel;
FIG. 6 is a cross-sectional view showing the structure of FIG. 5 assembled;
FIG. 7 is a top plan view, partially in section, showing the structure of FIGS. 5 and 6; and
FIG. 8 is a top plan view, partially in section, showing the structure of FIG. 7 during impact of the bumper with an object.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawing, and in particular, FIGS. 1 and 2, there is shown a portion of the right rear section of an automobile having a body panel 10 and bumper 12. The bumper 12 is mounted onto the automobile frame by shock-absorbing means, which may be of any type well known in the art, providing for the bumper to move inwardly toward the vehicle body (and the panel 10) upon impact as shown in FIG. 2, and to return to its normal position upon release of the impact force, as shown in FIG. 1.
As will be observed in FIGS. 1 and 2, the bumper 12 is provided with a trim molding 14 which is fixed to the bumper in alignment with a similar trim molding 16 mounted on the panel 10. Although the trim molding 16 could be of continuous cross-section, in the present embodiment, it has a portion removed to reveal a reflector or light source 18 mounted on the panel.
In order to provide a smooth appearance between the bumper 12 and the panel 10, a channel-shaped transition member 19 of polyeurethane, or other flexible plastic material, is mounted between the panel 10 and the bumper 12, and is generally of the same color as that of the automobile body panel 10. As will be noted in FIG. 2, the member 19 is mounted to flex when the bumper 12 is moved inwardly toward the panel 10, but returns to its original configuration (as shown in FIG. 1) when the force of impact is removed from the bumper.
In order to locate the molding 16 in close relation to the bumper 12 and, thereby, to prevent an unsightly gap occuring between the otherwise continuous molding members, the molding 16 is mounted such that it deflects away from the body panel 10 when the bumper 12 is forced inwardly upon impact, and returns to its original position when the force of impact is removed.
To provide a flexible mounting for the molding 16, there is provided a retaining device 20. The retaining device 20, as best shown in FIGS. 3 and 4, comprises one resilient member 22 formed of metallic material, such as spring steel. In the present embodiment, the member 22 is formed of SAE 1050 spring steel material, 0.041 inches thick. The device 20 further comprises a second resilient member 24, which is of non-metallic material. In the embodiment shown, the member 24 is manufactured of type 6-6 nylon and is of similar configuration to the member 22, in plan form.
The metallic member 22 has a continuous slot 26 extending from adjacent one end of the member to a point near the opposite end to form a resilient tongue 28. A threaded male fastener 30 is affixed at a point near the distal end of the tongue 28, and the tongue is curved outwardly from its point of origin which lies in the plane of periphery of the member 22 to the distal end of the tongue, which also lies substantially in the plane of the periphery of the member 22.
Referring still to FIGS. 3 and 4, the non-metallic member 24 is similarly formed to provide a tongue 32 having substantially the same plan form as the tongue 28. An elongated opening 33 is provided in the tongue 32 for receiving the fastener 30 therethrough when the members 22 and 24 are assembled to form the retainer device 20. A pair of upstanding tabs 34 and 35 are formed at opposite ends of the member 24 and four substantially L-shaped tabs 36, 37, 38 and 39 are formed in pairs adjacent either end of the member 24 to receive the resilient metallic member 22 in interfitting engagement, and thus to form the retaining device 20.
At that portion of the member 24 near the distal end of the tongue 32, there is located a pair of outwardly extending land elements 40 and 42 on which the edges of a trim strip are supported when the retaining device 20 is in the assembled position. At the opposite end of the member 24, a pair of outwardly extending flanges 44 and 46 provide means for retaining a flanged trim strip onto that end of the device 20. Both the lands 40 and 42 and the flanges 44 and 46 extend substantially the same distance outwardly from the member 24, the flanges being retained within the trim strip and the land being retained adjacent the panel 10, to support the strip adjacent the panel.
As shown in FIG. 4, initial assembly of the retaining device 20 is achieved by locating the resilient metallic member 22 under the L-shaped tabs 36 through 39 and within the bounds of the upstanding tabs 34 and 35. Ease of assembly is accomplished due to the flexibility of the non-metallic resilient member 24, which may be manufactured of nylon as described, or other plastic material. It will be observed that the two members 22 and 24, when assembled to form the retaining device 20, are of substantially the same dimensions in plan form, with the exception of the outwarding extending lands 40,42 and the flanges 44 and 46.
Referring now to FIGS. 5 and 6, the retaining device 20 is shown assembled in engagement with the molding 16 as it is prepared for installation onto the automobile panel 10.
The trim strip 16, employed in the present embodiment, comprises a metallic member 48 having flanges 49 and 50 turned inwardly, and a decorative portion 52 which is of plastic material, and may be of a contrasting or similar color to that of the automobile body. It will be obvious, however, that any configuration of the trim strip may be employed with the present invention, the primary requirement being the provision of flanges or similar retaining means similar to the flanges 49 and 50.
As will be noted from FIGS. 5 and 6, the retaining device 20 is attached to the trim molding 16 by inserting the flanges 44 and 46 of the member 20 within the opening provided by the flanges 49 and 50 of the molding 16, with the lands 40 and 42 in engagement with the outer portions of the flanges 49 and 50.
To attach the retaining device 20, and the molding 16 secured thereto, to the automobile body panel 10, a hole 54 is drilled through the panel 10 and the fastener 30 is received therethrough. A sealing washer 56 is located between the retaining device 20 and the panel 10, and a metal washer 58 and nut 60 engage the fastener on the opposite side of the panel to firmly affix the retaining device and molding to the panel.
Referring now to FIGS. 7 and 8, it will be noted that in the assembled unstressed state, as in FIG. 7, the members 22 and 24 of the retaining device 20 are substantially parallel to the panel 10. That is, the curved portion of the tongue 28 is forced toward the panel 10 by virtue of the fastener 30 and nut 60 to cause a pre-tension in the tongue 28 which is effective substantially over the length of the tongue 28 to force the retaining device 20 and the molding 16 against the panel 10.
In FIG. 8, it will be seen that upon impact of an object with the bumper 12, the bumper moves inwardly toward the panel 10, with the resultant buckling of the transition member 19. In the embodiment shown, the outward buckling of the member 19 forces the molding 16 away from the body panel 10 and prevents buckling of the molding which would occur should the bumper 12 or its molding 14 contact the molding 16. It will be noted that movement of the molding 16 causes the tongue 28 of the resilient member 22 to be flexed away from the panel 10. The flexure takes place over the greater length of the retaining device 20 and therefore, there are no sharp bends produced in the molding 16, tending to buckle the molding. In fact, the molding 16, by virtue of the support provided at the end thereof, and the length over which it is moved away from the panel 10, is not subjected to sharp bending which would cause distortion or permanent injury to the molding 16.
When the load is removed from the bumper 12, the bumper will return to its original position, as will the transition member 19. The tongue 28, having a pre-stress applied to it in its original position shown in FIG. 7, serves to bring the trim strip 16 into the position shown in FIG. 7 and will continue to perform this function over a number of cycles.
In addition, the non-metallic resilient member 24 serves two functions, that of isolating the metallic member 22 from the metal panel 10 to prevent corrosion between the metallic elements, and further provides a non-metallic pad at the lands 40 and 42 and the flanges 44 and 46 which align the molding 16 with the device 20 and serve to protect the paint or finish of the panel 10 when the retaining device 20 and trim molding 16 snap back into the position shown in FIG. 7.
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A device is provided for resiliently retaining an end portion of a decorative trim molding onto an automobile body panel wherein the molding is aligned with a similar molding on a bumper member, the bumper member being mounted for movement relative to the automobile body, on impact. The device allows the end portion of the molding member to move outwardly from the body a distance to allow the aligned molding on the bumper to move past it, thereby preventing buckling of the body panel molding. The device is effective to return the molding to the aligned position on the body after a plurality of such impacts.
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FIELD OF THE INVENTION
[0001] The present invention is generally directed to a process for recycling paper broke containing a wet strength additive. More particularly, the present invention is directed to a process for recycling paper broke containing a wet strength additive by mechanically fiberizing the broke into substantially discreet fibers. Once recycled into discreet fibers, the broke can then be used in forming any paper product, such as wipers and tissues.
BACKGROUND OF THE INVENTION
[0002] During the production of tissue and paper products, significant amounts of scrap material are accumulated. This waste product, also known as broke, is generated from products that do not fall within manufacturer's specifications or from excess paper remaining after the finished product is completed. Since broke is essentially unused raw material, a process to recycle it for future use would eliminate the inefficient disposal of a valuable source of papermaking fibers.
[0003] Problems have been experienced in the past, however, in being able to reuse the paper fibers contained in broke. For instance, prior to using broke for making a commercial tissue, wiper or other similar product, it is necessary to treat the fiber source to chemically degrade unwanted chemical constituents which may adversely affect the quality of the recycled paper product. Notable examples of contaminants that must be removed from broke before the broke can be recycled are wet strength additives. Wet strength additives are added to fibers during the wet end process of the papermaking procedure to increase the strength of tissue and paper products when wet. Examples of wet strength additives include but are not limited to polyamines, urea-formaldehyde, melamine-formaldehyde, alkaline-curing polymeric amine-epichlorohydrine, ketene dimers and glyoxalated polyacrylamide resin.
[0004] Historically, permanent wet strength broke has been broken down and recycled using chemical processes. Specifically, there have been three types of chemical processes employed for repulping permanent wet strength broke. The purpose of each of the chemical treatments is to aid in degrading the wet strength chemistry so the mechanical action of the pulper rotor can degrade the tissue or paper into individual fibers suitable for reuse in other products. The first and most effective of these chemical processes to remove wet strength additives includes treating the broke with hypochlorite, chlorine, or hypochlorous acid, depending on reaction conditions in the hydrapulper, to chemically oxidize the wet strength resin molecule and thus allow the tissue to be further broken down by the shearing and mechanical action of the pulper rotor. The disadvantages of this process include potential chloroform generation, loss of brightness on unbleached fiber, and increased potential for corrosion of the paper machine.
[0005] Another chemical process entails treatment of the fiber with caustic and high temperature to swell the wet strength tissue structure such that the mechanical action of the hydrapulper can defiberize the sheet. Although this process is effective on unbleached grades of fiber, the disadvantages of this procedure are the need for heating the pulpers and the handling of caustic treatments. Caustic can also darken the fibers.
[0006] Finally, the third chemical process for repulping permanent wet strength broke includes treating the broke with persulfate salts. As with the other chemical procedures, the treatment with persulfate salts possesses disadvantages such as the need to neutralize residual persulfate, the need for pH and temperature adjustment, and the high cost of chemicals.
[0007] Using chemical processes to prepare wet strength broke for recycling can be expensive because of the additional cost of chemicals described in the aforementioned processes. In addition, there are certain types of fibers which cannot be successfully defibered using chemical treatments in the wet state. Also, there are certain grades of wet strength additives that may not be adequately defibered by chemical treatment. Finally, chemical treatments may have unfavorable reactions with the fiber. An example of such a chemical interaction is the yellowing that occurs when mechanically pulped fibers are contacted with hypochlorite, chlorine, hypochlorous acid, or caustic (sodium hydroxide).
[0008] Accordingly, there remains a need for a fiberizing process for broke containing wet strength additives that avoids the use of chemical treatments in the wet state.
SUMMARY OF THE INVENTION
[0009] The present invention recognizes and addresses the foregoing drawbacks, and deficiencies of prior art constructions and methods.
[0010] Accordingly, it is an object of the present invention to provide an improved method for recycling broke containing wet strength additives.
[0011] Another object of the present invention is to provide a process for recycling broke containing wet strength additives without having to chemically treat the broke.
[0012] It is another object of the present invention to provide a method for recycling broke containing wet strength additives by mechanically fiberizing the broke.
[0013] Still another object of the present invention is to provide a process for mechanically recycling broke containing a wet strength additive for forming paper products, such as wipers and tissues.
[0014] These and other objects of the present invention are accomplished by providing a process for recycling paper containing wet strength additives. The paper containing the wet strength additives can be broke obtained from, for instance, wipers, tissues and other similar paper products. According to the present invention, the paper containing the wet strength additive is mechanically fiberized for a time sufficient to overcome fiber bonds formed by the wet strength additives. Ultimately, the paper is fiberized into substantially discreet fibers. The discreet fibers can then be re-incorporated into a fiber furnish for forming a paper web, which can then be used in forming various products.
[0015] The process of the present invention can be used to process papers containing any amount of a wet strength additive. For most applications, however, the paper will contain from about 0.5% to about 5% by weight of the wet strength additive and particularly from about 0.5% to about 2% of the wet strength additive. The wet strength additives present in the paper can vary depending upon the particular application. Examples of wet strength additives include polyamines, urea-formaldehydes, melamine-formaldehydes, epichlorohydrines, ketene dimers, and polyacrylamide resins.
[0016] Prior to being fiberized, the paper containing the wet strength additive can be dried and shredded if desired. In general, the paper being fiberized should have a moisture content of less than about 20%, and particularly less than about 15%. Preferably, the paper has a moisture content that is about the same as or less than the moisture content of the atmosphere.
[0017] Various devices can be used in order to mechanically fiberize the paper. In general, a mill or pulverizer is used in the process. Specific examples of mills that can be used include a hammermill, a disc mill, a pin mill or a wing beater mill.
[0018] Once the paper is recycled into discreet fibers, the fibers can be used to form various products. For instance, the fibers can be incorporated into an aqueous fiber furnish and used to form various paper webs. The fiber furnish can contain recycled broke alone or in combination with other various types of fibers. Products that can be made with the recycled broke include wipers, tissues, and various other similar products.
[0019] Other objects, features and aspects of the present invention are discussed in greater detail below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] A full and enabling disclosure of the present invention, including the best mode thereof to one of ordinary skill in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying figures in which:
[0021] [0021]FIG. 1 is a perspective view of an example of a fiberizer apparatus used to carry out the process of the present invention.
[0022] [0022]FIG. 2 is a perspective view of the fiberizer of the type shown in FIG. 1 with the front lid opened to expose the impeller blades and serrated working surface.
[0023] [0023]FIG. 3 is a cut-a-way perspective view of the opened fiberizer with the impeller removed to expose the orifice through which the processed fibers are withdrawn from the working chamber.
[0024] [0024]FIG. 4 is a side elevation of the fiberizer partially in section illustrating its operation.
[0025] [0025]FIG. 5 is a perspective view of a fiberizer modified to operate in a continuous mode.
[0026] [0026]FIG. 6 is a schematic flow diagram illustrating a process in accordance with this invention.
[0027] Repeat use of reference characters in the present specification and drawings is intended to represent same or analogous features or elements of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended to limit the broader aspects of the present invention which broader aspects are embodied in the exemplary construction.
[0029] The present invention embodies the use of a dry mechanical treatment for reworking wet strength broke in preparation for reuse in tissue and other paper products, thus avoiding the need for chemical treatment in the wet state. In general, the invention resides in a method for dry fiberizing waste broke comprising wet strength additives by first mechanically fiberizing a wet strength additive-bearing broke source in a substantially dry state, preferably air dry, thereby producing discrete fibers. As used herein, “air dry” refers to the moisture content of the broke being in equilibrium with atmospheric conditions to which it is exposed. Next, the dry fibers are redispersed in water to form a slurry for the preparation of tissue or paper products.
[0030] According to the present invention, fiberization is conducted when the wet strength broke is air dry or otherwise substantially dry. In one specific embodiment of the invention, a Pallmann pulverizer is used for defibering the wet strength broke. Other equipment such as a hammermill or similar type of mechanical fiberizing equipment may be used.
[0031] An example of a fiberizing apparatus that may be used in the process of the present invention is disclosed in U.S. Pat. No. 4,668,339 to Terry which is incorporated herein by reference in its entirety. Other fiberizing processes are also disclosed in U.S. Pat. No. 4,867,383 and U.S. Pat. No. 4,615,767, which are both incorporated herein by reference. The prior patents are primarily directed to a process for removing ink-bearing fines from various fiber sources. None of these references, however, disclose or suggest dry fiberizing paper containing wet strength additives in order to recycle the fibers contained within the paper. In fact, as discussed above, in the past it has been taught to chemically treat paper containing wet strength additives in order to recycle the paper.
[0032] Once the dry fiberization process has been completed, the individual fibers can be re-dispersed in a water slurry of 3-5% consistency in a stock chest. The broke fibers can then be blended with the other furnish components and used to produce tissue, wipes or other similar paper products. Tissue or paper made from the resultant mechanically defibered broke is characterized as having higher bulk, porosity, opacity, and brightness than tissue or paper made from conventionally chemically reworked broke. Including the elimination of additional chemical costs, the dry fiberization process can also be used on any furnish type without discoloring pulps. Also, the present invention is independent of the level of wet strength in the product or type of wet strength resin used with the product.
[0033] The fiberization apparatus illustrated in FIG. 1, a turbomill, represents one example of a fiberizer that may be used in the present invention. However, those skilled in the art may use a variety of fiberization apparatus units available to carry out the process of this invention, such as a Pallmann pulverizer, hammermills, disc mills, pin mills, wing beater mills, etc. In general in FIG. 1, the fiberizer 1 comprises a housing which encloses rotating rotor blades (See FIG. 2) driven by a suitable drive means 2 . The wet strength broke, which may be shredded, is fed through feed inlet 3 and the waste paper is comminuted or fiberized substantially to individual fibers. An internally disposed fan draws air in through the feed inlet 3 along with the waste paper, and expels the air through exit port 4 carrying the fibers along with the air. The fibers are collected in a tubular meshed bag 5 or other suitable container. Also shown in FIG. 1 is cooling means having water supply inlet 6 and exit ports 7 for removing heat generated due to friction by the shearing of the fiber feedstock.
[0034] [0034]FIG. 2 illustrates the internal working chamber of the fiberizer, primarily illustrating the position of the rotor blades. There is shown a serrated, grooved working surface 8 against which the feed material is abraded by the action of the moving rotor blades 9 . Although not clearly shown in this Figure, there is a space between the serrated working surface and the blades in which cellulosic materials are buffered about. The blade position relative to the working surface 8 is adjustable to add a degree of control over the extent of fiberization, which is also controlled by the rotor speed, the residence time, the gap between the rotor and the stator, and the nature of the working surface.
[0035] The working surface 8 consists of six removable segments. These can be replaced by a greater or fewer number of segments having a different design or configuration with respect to the surface. This flexibility provides an infinite number of choices for altering and optimizing the fiberization. More specifically, the grooves of each segment as shown are parallel to each other and are spaced apart by about 2 millimeters (mm), measured peak-to-peak. Each groove is about 1.5 mm deep. The radial width of each segment is about 10 centimeters (cm). These dimensions are given only for purposes of illustration and are not limiting, however. Also, partially shown is the working surface on the inside of the hinged cover 10 , which is substantially identical to the other working surface 8 already described. When the cover is closed, the two working surfaces provide an inner chamber in which the feed material is fiberized.
[0036] [0036]FIG. 3 is a cut-a-way perspective of the fiberizer with the rotor removed to expose the orifice 11 through which the fiberized material passes before exiting through the exit port 4 . The size of the orifice is variable which controls the degree of fiberization by increasing or decreasing the air flow rate and hence the residence time within the fiberizer. The orifice is contained within a removable plate 12 for convenient changing of the orifice size. An orifice diameter of 160 mm has been found to be suitable in conjunction with an air flow rate of about 10 cubic meters per minute. Also shown in FIG. 3 are the impeller blades 13 of the fan which provides the flow of air through the fiberizer.
[0037] [0037]FIG. 4 is a cross-sectional, cut-a-way view of the fiberizer schematically illustrating its operation. The arrows indicate the direction of flow of air and fibers. More specifically, the wet strength broke source 15 is introduced into the feed inlet 3 where it is contacted by the rotating blades 9 . The air flow directs the wet strength broke between the rotor blades and the working surface 8 such that the wet strength broke is comminuted into smaller and smaller particles, eventually being reduced or fiberized to substantially discrete fibers. The centrifugal forces created by the rotor blades tend to force the particles, preferentially the larger particles, to the apex 16 between the angled working surfaces. These forces tend to keep the larger particles from escaping before they have been completely fiberized. Upon substantially complete fiberization, the comminuted solid materials are carried through the orifice 11 of the removable plate 12 . The fan impellers 13 then force the airborne fibers out through the exit port 4 .
[0038] [0038]FIG. 5 illustrates the operation of the fiberizer previously described, but slightly modified for continuous operation as would likely be required for commercial operation. In this embodiment, the feed inlet 3 is shown as a tubular inlet rather than the hopper as shown in FIG. 1. The feed tube will provide a continuous supply of shredded wet strength broke material of suitable size and quality. Generally speaking, such a material can be in the form of sheets from about 2 to about 4 inches square or less and should be free of debris to protect the fiberization apparatus. However, the particle size and shape of the feed will depend on the capabilities of the particular fiberizer being used and is not a limitation of this invention.
[0039] A further modification illustrated is the continuously moving screen 18 which collects the fibers in the form of a web or batt 19 . Shown in phantom lines is a modified exit port 4 which has been widened to accommodate the width of the moving screen.
[0040] In one embodiment, the fiberizer is configured to receive broke at a rate of at least 1.5 pounds per minute. In this embodiment, the fiberizer can be set up with a 3 mm clearance between the serrated working surface and the rotor blades. A removable plate having an orifice of 140 mm can be installed behind the impeller, which travels at, for instance, 4830 revolutions per minute (r.p.m.) with no load. Air flow through the fiberizer can be about 365 cubic feet per minute. Cooling water can be fed to the cooling jacket at the rate of 2 liters per minute. Typically, the initial water temperature will be 59-60 degrees Fahrenheit (F.) and will level off at 66-68 F. after an extended run. The speed of the wire receiving the fiberized material from the fiberizer can be set at 350 feet per minute.
[0041] [0041]FIG. 6 schematically illustrates an overall view of a process in accordance with this invention. More particularly, it shows a source of wet strength broke 15 being fed to a fiberizer 21 identical to or similar in function to the type described in the previous Figures. In the fiberizer the wet strength broke, whether shredded or not, is substantially reduced to individual or discrete fibers and deposited on a moving screen 18 . Deposition of the fibers onto the screen is aided by a vacuum box 20 . The fibrous mass or batt of fibers deposited on the moving screen is thereafter recovered by metering to a uniform thickness in a suitable metering device 24 and thereafter converted into bales of pulp in a baler 25 or, alternatively, fed directly into a pulper to form a pulp slurry for making paper in the conventional manner. In addition, the recovered fibers can be fed directly to an air-forming apparatus for producing air laid webs or batts. Those skilled in the art will recognize that a variety of apparatus or equipment can be used in performing the functions illustrated herein.
EXAMPLES
[0042] In order to illustrate the effectiveness of the process of the present invention, dry fiberizing of a wet strength broke source in accordance with the present invention was carried out using a pulverizer as the fiberizer apparatus. Additional wet strength broke of the same source was also wet fiberized using hypo bleach to compare the two processes against one another. The wet strength broke source originated from SCOTT towels. The results are set forth in Table I below.
[0043] The properties of the SCOTT® towel broke that was used in the example are as follows:
Basis Weight of Towel 23.5 lbs/2880 sq. ft. Furnish 20% hardwood Kraft 60% softwood Kraft 20% Broke Kymene additive level 1.0% (20 lbs/ton) (wet strength additive)
[0044] After the broke was reduced to individual fibers using the hypo bleach process and the dry fiberizing process of the present invention, paper hand sheets were formed from the fibers and tested. In particular, the hand sheets were tested for their drainage properties (Canadian Standard Freeness TAPPI test), for tensile strength, for stretch characteristics, for slope, for caliper, for tear resistance, for porosity, for brightness using an Elrepho Photoelectric Reflectance Photometer, for opacity, and for weighted average fiber length (WAFL) which was determined using a Kajaani FS-200 device. The above tests performed were standard tests essentially conforming to TAPPI standard procedure numbers X, Y, Z, A, B, C, D and E, respectively as would be known to one skilled in the art and were used for comparative purposes. The following results were obtained:
TABLE 1 Wet Fiberized Sample “Control” Dry Fiberized Freeness (ml) 670 790 Tensile (NM/g) 23.06 3.31 Stretch (%) 2.16 0.86 Tensile (gcm/cm 2 ) 22.64 0.87 Energy Absorbed (TEA) Slope A (kg) 480.0 0.0 Caliper (in) 0.0066 0.0090 Tear (gf) 89.83 14.23 Porosity (ft 3 /min/ 194.0 934.4 ft 2 ) Brightness (ISO, %) 69.82 76.41 L* 92.51 93.60 a* −1.75 −1.22 b* 10.21 6.51 Opacity (%) 76.01 78.23 WAFL (mm) 1.86 1.69
[0045] As shown above, in comparison to chemically defibering the broke, the dry fiberization process of the present invention substantially increases freeness and bulk. Further, fibers produced in accordance to the process of the present invention also yielded hand sheets with better brightness and opacity characteristics. The dry fiberization process of the present invention has the potential to produce high bulk, high brightness debonded fibers, in comparison to traditional methods. Further, these improvements are realized at a lower cost and without having to handle the chemicals used in the past.
[0046] These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.
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The present invention is generally directed to a process for recycling paper containing wet strength additives. The process generally includes the step of mechanically fiberizing the paper in order to reduce the paper into substantially discreet fibers. The paper can be fiberized in various devices, including mills and pulverizers. Once the paper has been converted into substantially discreet fibers, the fibers can then be used in forming various paper products, including wipers and tissues. Of particular advantage, it has been discovered that fibers produced according to the process of the present invention produce paper webs having high bulk, high brightness, high porosity, and high opacity.
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This application is a continuation of application Ser. No. 08/188,223, filed on Jan. 27, 1994 now U.S. Pat. No. 5,688,506.
BACKGROUND OF THE INVENTION
Gonadotropin Releasing Hormone ("GnRH", also known as Luteinizing Hormone Releasing Hormone, or "LHRH"), is of central importance to the regulation of fertility. Johnson M., Everitt B. Essential Reproduction, 3rd Edn. Blackwell Scientific Publications, 1988. In males and females, GnRH is released from the hypothalamus into the bloodstream and travels via the blood to the pituitary, where it induces the release of the gonadotropins, luteinizing hormone and follicle stimulating hormone, by gonadotroph cells. These two gonadotropins, in turn, act upon the gonads, inducing steroidogenesis and gametogenesis. Steroids released from the gonads into the circulation subsequently act upon various tissues.
The gonadotropin hormonal cascade can be halted by neutralization of the biological activity of GnRH. Fraser H. M. Physiological Effects of Antibody to Leutenizing Hormone Releasing Hormone. In: Physiological Effects of Immunity Against Reproductive Hormones, Edwards and Johnson, Eds. Cambridge University Press, 1976. As a consequence of GnRH neutralization, the gonadotropins and gonadal steroids are not released into the blood and their biological activities are thereby eliminated. By eliminating the biological activity of GnRH, the hormonal regulation of fertility is interrupted and gametogenesis ceases. GnRH neutralization halts the production of gametes. GnRH neutralization is thus an effective means of contraception.
A number of important diseases are affected by gonadotropins and gonadal steroid hormones, particularly the gonadal steroids. Such diseases include breast cancer, uterine and other gynecological cancers, endometriosis, uterine fibroids, prostate cancer and benign prostatic hypertrophy, among others. Removal of the gonadal steroid hormonal stimuli for these diseases constitutes an important means of therapy. An effective method of accomplishing this is by neutralizing GnRH, the consequence of which is the elimination of gonadal steroids that induce and stimulate these diseases. McLachlan R. I., Healy D. L., Burger G. B. 1986. Clinical Aspects of LHRH Analogues in Gynecology: a Review, British Journal of Obstetrics and Gynecology, 93:431-454. Conn P. M., Crowley W. F. 1991. Gonadotropin-Releasing Hormone and Its Analogs, New England Journal of Medicine. 324:93-103. Filicori M., Flamigni C. 1988. GnRH Agonists and Antagonists, Current Clinical Status. Drugs. 35:63-82.
One effective means of neutralizing GnRH is the induction or introduction of anti-GnRH antibodies in the host or patient. Such antibodies can be induced by active immunization with GnRH immunogens or by passive immunization by administering anti-GnRH antibodies. Fraser H. M. Physiological Effects of Antibody to Leutenizing Hormone Releasing Hormone. In: Physiological Effects of Immunity Against Reproductive Hormones, Edwards and Johnson, Eds. Cambridge University Press, 1976. Since anti-GnRH antibodies can neutralize the biological activity of GnRH, immunization constitutes an important approach towards treating diseases dependent upon gonadal steroids and other reproductive hormones as well as a means to regulate mammalian fertility.
GnRH has the same amino acid sequence in all mammals (pGlu-His-Trp-Ser-Tyr-Gly-Leu-Arg-Pro-GlyNH 2 ) (SEQ ID NO.: 1 in the Sequence Listing), thus a single immunogen would be effective in all mammalian species, including humans. Active immunization against GnRH, however, has not been practicable due to deficiencies associated with the GnRH immunogens. The prior art anti-GnRH immunogens are not of sufficient potency, and therefore must be administered repeatedly to induce effective levels of anti-GnRH antibodies. In addition, they have not proven to be reliable, in terms of inducing anti-GnRH antibodies in an acceptable portion of the immunized population.
SUMMARY OF THE INVENTION
The present invention, concerns improved immunogens against GnRH that induce neutralizing titers of anti-GnRH antibodies in response to a single administration of immunogen in all of the immunized populations that we have studied. The immunogens of the invention may thus be used to treat steroid dependent diseases and may also be used as immunocontraceptives to regulate fertility.
The immunogens of the present invention are peptides composed of two functional regions: the immunomimic region and a spacer region. The function of the immunomimic which immunologically crossreacts with GnRH is to induce antibodies that bind to the targeted hormone. The spacer element of the peptide serves as a link through which the immunomimic is attached to an immunological carrier, such as diphtheria toxoid ("DT") and also affects the immune response generated by the vaccinated mammal against the immunomimic. For example, in a specific embodiment of the invention, the immunogen peptide has the sequence: pGlu-His-Trp-Ser-Tyr-Gly-Leu-Arg-Pro-Gly-Arg-Pro-Pro-Pro-Pro-Cys (SEQ ID NO: 2 in the Sequence Listing). In this ("GnRH(1-10)-Arg10") peptide, the sequence pGlu-His-Trp-Ser-Tyr-Gly-Leu-Arg-Pro-Gly-- (SEQ ID NO: 3 in the Sequence Listing), comprises the immunomimic of GnRH. The remainder of the peptide's sequence, --Arg-Pro-Pro-Pro-Pro-Cys (SEQ ID NO: 4 in the Sequence Listing), constitutes the spacer, which is attached to amino acid number 10 of the GnRH immunomimic.
A preferred embodiment of the invention concerns two peptide immunomimics of GnRH that are associated with four spacer sequences. Methods of coupling these peptides to immunological carriers, such as DT, to yield anti-GnRH immunogens are provided. The immunogens may be used singly or in combination to induce anti-GnRH antibody responses in the vaccinated mammal. As compared to the prior art anti-GnRH immunogens, the immunogens of the present invention induce a biologically effective immune response following a single administration of immunogen in all of the immunized animals tested. The immunogens can be administered in different physical forms, including soluble and precipitate. The immunomimic spacer peptides of this invention can be coupled to immunological carriers over a wide range of peptide to carrier substitution ratios and yield effective immunogens.
The invention also concerns methods of treating gonadotropin and gonadal steroid hormone dependent diseases and cancers by immunization with the immunogens of the invention. A specific embodiment of the invention concerns a method of immunological contraception in mammals comprising the administration of the inventive immunogens.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1: Depicts anti-GnRH antibody responses to the administration of the inventive immunogens comprising peptides 1-4 and the comparative prior art anti-GnRH immunogen, peptide 5 as measured by mean antigen binding capacities ("ABC") in pico moles per milliliter with respect to days after immunization in immunized rabbits.
FIG. 2: Depicts the antibody response to immunization with an immunogen comprising a mixture of peptides 3 and 4 as measured by mean ABC with respect to days after immunization.
FIG. 3: Depicts the results of immunizations in mice as measured by a mean ABC with respect to days after immunization after immunization with fractions of a preparation of peptide 2 immunogens fractionated on the basis of solubility.
FIG. 4: Depicts antibody responses in mice as measured by mean ABC with respect to days after immunization when immunized with various conjugates of peptides 1 and 2 at different peptide: DT substitution ratios.
FIG. 5: Depicts antibody responses of male rabbits as measured by mean ABC with respect to days after immunization when immunized with a mixture of conjugates of peptides 1 and 2. Serum testosterone levels in these male rabbits over the course of the immunization test period are shown.
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLE 1
Peptides with the amino acid sequences listed in Table 1 were synthesized and prepared by standard solid phase synthesis methods. Each peptide was characterized as to amino acid content and purity.
TABLE 1__________________________________________________________________________PeptideDesignation Amino Acid Sequence__________________________________________________________________________1 GnRH(1-10)-Ser1 Cys--Pro--Pro--Pro--Pro--Ser--Ser--Glu--His-- Trp--Ser--Tyr--Gly--Leu--Arg--Pro-- Gly(NH.sub.2)(SEQ ID NO: 5 in the Sequence Listing) 2 GnRH(1-10)-Ser10 pGlu--His--Trp--Ser--Tyr--Gly--Leu--Arg-- Pro--Gly--Ser--Ser--Pro--Pro--Pro--Pro--Cys (SEQ ID NO: 6 in the Sequence Listing) 3 GnRH(1-10)-Arg1 Cys--Pro--Pro--Pro--Pro--Arg--Glu--His--Trp-- Ser--Tyr--Gly--Leu--Arg--Pro--Gly(NH.sub.2) (SEQ ID NO: 7 in the Sequence Listing) 4 GnRH(1-10)-Arg10 pGlu--His--Trp--Ser--Tyr--Gly--Leu--Arg-- Pro--Gly--Arg--Pro--Pro--Pro--Pro--Cys (SEQ ID NO: 2 in the Sequence Listing)__________________________________________________________________________
Each of peptides 1-4 contains an immunomimic of GnRH that is either preceded by or followed by a spacer. Two immunomimics of GnRH were used: pGlu-His-Trp-Ser-Tyr-Gly-Leu-Arg-Pro-Gly-- (SEQ ID NO: 3 in the Sequence Listing), (peptides 2 and 4 Table 1) wherein the spacer was attached through the carboxy terminal end of GnRH (amino acid #10); and, --Glu-His-Trp-Ser-Tyr-Gly-Leu-Arg-Pro-Gly(NH 2 ) (SEQ ID NO: 8 in the Sequence Listing), (peptides 1 and 3 Table 1) wherein the spacer was attached at the amino terminal end of GnRH (amino acid #1).
The four spacers set forth in Table 2 were used.
TABLE 2______________________________________Spacer Designation Amino Acid Sequence______________________________________Ser 1 Cys--Pro--Pro--Pro--Pro--Ser--Ser-- (SEQ ID NO: 9 in the Sequence Listing) Ser 10 --Ser--Ser--Pro--Pro--Pro--Pro--Cys (SEQ ID NO: 10 in the Sequence Listing) Arg 1 Cys--Pro--Pro--Pro--Pro--Arg-- (SEQ ID NO: 11 in the Sequence Listing) Arg 10 --Arg--Pro--Pro--Pro--Pro--Cys (SEQ ID NO: 4 in the Sequence Listing)______________________________________
The numerals 1 and 10 in the spacer designation refer to the GnRH amino acid number to which the spacer is attached. While these spacer regions of the molecules have been set forth separately in Table 2, in the preferred embodiment of the invention the peptide is synthesized as one continuous peptide sequence molecule.
Each of these peptides 1-4 of Table 1 was conjugated to amino groups present on a carrier such as Diphtheria Toxoid ("DT") via the terminal peptide cysteine residue utilizing heterobifunctional linking agents containing a succinimidyl ester at one end and maleimide at the other end of the linking agent.
To accomplish the linkage between any of the Peptides 1-4 above and the carrier, the cysteine of the peptide was first reduced. The dry peptide was dissolved in 0.1 M sodium phosphate buffer (degassed), pH 8.0, with a thirty molar excess of dithiothreitol ("DTT"). The solution was stirred under a water saturated nitrogen gas atmosphere for three hours at room temperature. An additional 15 molar excess DTT was added and the mixture was stirred an additional hour at room temperature under water saturated nitrogen gas. The peptide containing reduced cysteine was separated from the other components by chromatography at 4° C. over a G10 Sephadex column equilibrated with 0.2 M acetic acid. The peptide was lyophilized and stored under vacuum until used.
The DT was activated for coupling to the peptide by treatment with the heterobifunctional linking agent epsilon-maleimidocaproic acid N-hydroxysuccinimide ester ("EMCS"), in proportions sufficient to achieve activation of approximately 25 free amino groups per 10 5 molecular weight of DT. In the specific instance of DT, this amounted to the addition of 6.18 mg of EMCS (purity 98%) to each 20 mg of DT.
Activation of DT was accomplished by dissolving each 20 mg aliquot of DT in 1 ml of 0.5 M sodium phosphate buffer, pH 6.6. Aliquots of 6.18 mg EMCS were dissolved into 0.2 ml of dimethylformamide. Under darkened conditions, the EMCS was added dropwise in 50 microliter ("μl") amounts to the DT with stirring. After 90 minutes incubation at room temperature in darkness, the mixture was chromatographed at 4° C. on a G50 Sephadex column equilibrated with 0.1 M sodium citrate buffer, pH 6.0, containing 0.1 mM ethylenediaminetetraacetic acid disodium salt ("EDTA"). (Column=1.5×120 cm; flow rate=8 ml/hr; fraction size=2 ml). The fractions' A 260 were determined using a spectrophotometer, enabling the fractions containing DT to be identified.
Fractions containing the EMCS activated DT were pressure concentrated over a PM 10 ultrafiltration membrane under nitrogen gas in conditions of darkness. The protein content of the concentrate was determined by the BCA method (PIERCE, Ill., USA). The EMCS content of the carrier was determined by incubation of the activated DT with cysteine-HCl followed by reaction with 100 μl of 10 mM Elman's Reagent (5, 5, dithio-bis (2-nitrobenzoic acid)). The optical density difference between a blank tube containing cysteine-HCl and the sample tube containing cysteine-HCl and carrier was translated into EMCS group content by using the molecular extinction coefficient of 13.6×10 3 for 5-thio-2-nitro-benzoic acid at 412 nm.
The reduced cysteine content ("-SH") of the peptide was also determined utilizing Elman's Reagent. Approximately 1 mg of peptide was dissolved in 1 ml of nitrogen gas saturated water and a 0.1 ml aliquot of this solution was reacted with Elman's Reagent. Utilizing the molar extinction coefficient of 5-thio-2-nitro-benzoic acid (13.6×10 3 ), the free cysteine -SH was calculated.
The reduced peptide was then coupled to the activated DT. An amount of peptide containing sufficient free -SH to react with a selected proportion of the EMCS activated amino groups on the DT was dissolved in 0.1 M sodium citrate buffer, pH 6.0, containing 0.1 mM EDTA, and added dropwise to the EMCS activated DT under darkened conditions. After all the peptide solution had been added to the activated DT, the mixture was incubated overnight in the dark under a water saturated nitrogen gas atmosphere at room temperature.
The conjugate of the peptide linked to DT via EMCS was separated from other components of the mixture by low pressure chromatography at 4° C. over a G50 Sephadex column equilibrated with 0.2 M ammonium bicarbonate (column=1.5×120 cm, flow rate=1.8 ml/15 min., fraction size=1.8 ml). The conjugate eluted in the column void volume (detected by A 280 measurements) and was lyophilized and stored desiccated at -20° C. until used.
The conjugate may be characterized as to peptide content by a number of methods known to those skilled in the art including weight gain, amino acid analysis, etc. Various substitution ratios of peptide to DT were accurately and reproducibly obtained by (1) varying the quantity of EMCS added to activate the DT, and/or, (2) varying the quantity of reduced peptide added to the EMCS activated DT. For example, the activation of DT with a ratio of 31 moles EMCS to 1 mole of 100,000 molecular weight DT adds 12±2 EMCS groups per 100,000 molecular weight of DT. The addition of 14 peptide groups per 100,000 molecular weight of this activated DT resulted in a substitution ratio of 12±2 peptides per 100,000 molecular weight of DT. Conjugates of Peptides 1-4 to DT produced by these methods were determined by amino acid analysis to have 4-30 moles of peptide per 10 5 MW of DT. All of the conjugates were considered suitable as immunogens for immunization of test animals.
EXAMPLE 2
For comparative purposes a prior art GnRH immunogen ("peptide 5") was constructed wherein the peptide immunomimic of GnRH did not contain a spacer element. Peptide 5 had the sequence: Glu-His-Trp-Ser-Tyr-Gly-Leu-Arg-Pro-GlyNH 2 (SEQ ID NO: 8 in the Sequence Listing).
The peptide was activated with m-Maleimidobenzoyl N-Hydroxysuccinimide Ester ("MBS"). 20.0 mg of [glu 1]-GnRH were dissolved in 1.0 ml of N,N-Dimethylformamide ("DMF"). To this solution was added 5.31 mg MBS dissolved in 1.0 ml DMF. The combined solution was stirred overnight at room temperature in the dark.
40.0 mg of DT was dissolved in 10.0 ml of Sodium Carbonate Buffer (0.2 M, pH=9.0), containing 2.2 mg of 2-Iminothiolane HCl ("2-IT"). The solution containing the MBS-activated GnRH was then slowly added to the DT/2-IT solution, and the mixture was stirred slowly for 8 hours at room temperature in the dark.
The conjugate was purified by column chromatography over Sephadex G50 (column: 1.5×100 cm; buffer: Ammonium Bicarbonate, 0.2 M; fractions: 2.6 ml, every 15 minutes) with identification of the fractions containing conjugate by spectrophotometry (A 254 ). G50 purified conjugate was lyophilized and stored desiccated at -20° C. until used. The peptide DT substitution ratio of the Immunogen 5 conjugate was determined by amino acid analysis to be 13 peptides per 10 5 molecular weight of DT.
EXAMPLE 3
Different groups of female rabbits were each immunized with one of the conjugates, peptides 1-5 of Examples 1 and 2. Each conjugate was dissolved to a concentration of 2.0 mg/ml in phosphate buffered saline (0.2 M, pH=7.2) containing 200 μg/ml of norMDP adjuvant. The conjugates comprising peptides 1,2,3 and 4 of Example 1 did not completely dissolve in the buffer; the conjugate of peptide 5 of Example 2 did completely dissolve in the buffer. Each mixture was emulsified with an equal volume of Squalene-Arlacel (4:1 ratio, volume of Squalene: volume of Arlacel) to prepare an immunogen formulation which contained 1.0 mg/ml conjugate and 100 μg/ml norMDP. 1.0 ml of immunogen was injected into each rabbit, administered into the rear leg muscles (2 sites, 0.5 ml/site), on day 0 of the test. Blood was collected from each rabbit prior to immunization on day 0, and on selected days thereafter. Serum was prepared from each blood sample and stored frozen at -20° C. until utilized in assays to determine the presence of anti-GnRH antibodies.
A liquid phase Radioimmunoassay (RIA) was used to detect and quantify anti-GnRH antibodies. In the RIA, 0.04, 0.2, 1.0 or 5.0 μl aliquots of antiserum were incubated with approximately 150 fmole of 3H labeled GnRH (specific activity=53.2 Ci/mmole) in a total volume of 400 μl. Dilutions were made in FTA Hemagglutination Buffer (BBL, Becton Dickinson Microbiology Systems, MD, USA) containing 1% bovine serum albumin. The antisera were incubated with labeled hormone for 2 hours at room temperature. A 0.1 ml aliquot of heat inactivated (56° C., 30 min) fetal calf serum (cooled to 2-8° C.) was then added to each tube, following which the antibody-hormone complexes were precipitated by the addition of 0.5 ml of 25% polyethylene glycol (MW=8,000 gm/mole) (cooled to 2-8° C.). The precipitates were pelleted by centrifugation (30 minutes at 1500×g), the supernatants were discarded, and the pellets were counted by liquid scintillation counting to measure the quantity of radioactivity contained therein. Antigen binding capacities (ABC) for each antiserum were then determined from the amount of radioactive hormone precipitate after subtraction of nonspecific background binding (determined by preincubation of the antisera dilution with excess amounts (˜10 5 fold) of the hormone). Inhibition of the antisera with the excess quantity of unlabeled hormone also established the specificity of the antisera for GnRH. Serum taken from the rabbits prior to immunization served as nonimmunized (normal) controls.
The mean ABCs measured in the sera from rabbits immunized with the conjugated peptides of Examples 1 and 2 are shown in Table 3 and in FIG. 1. As the results show, a single administration of the immunogens comprising peptides 1,2,3 and 4 of Example 1 induced rapid and potent antibody responses against GnRH.
TABLE 3__________________________________________________________________________RABBIT ANTI-GNRH ANTIBODY RESPONSES INDUCED BY ONE ADMINISTRATION OF PEPTIDE CONJUGATE Peptide:DT Substitution Rabbit Sera ABC (mean) [pmoles/ml]Peptide Ratio Day 0 Day 14 Day 21 Day 28 Day 36 Day 44 Day 56 Day 73 Day 85 Day 105__________________________________________________________________________ 1 13 0 0.30 10.83 22.63 57.23 68.93 72.13 61.23 58.73 54.03 2 13 0 0.27 7.52 19.83 57.63 77.83 78.73 60.83 47.90 24.93 5 13 0 0 0 1.78 1.60 1.51 2.00 2.10 Day 0 Day 15 Day 24 Day 31 Day 44 Day 59 Day 79 Day 101 3 11 0 1.53 24.59 58.31 102.71 118.16 120.99 61.00 4 13 0 1.77 8.90 26.03 42.88 38.25 38.30 24.35__________________________________________________________________________ n = 5 rabbits for Peptides 1, 2, 3 and 4. n = 6 rabbits for peptide 5.
By comparison, the anti-GnRH response induced by a single administration of the peptide 5 immunogen of Example 2 induced a minimal response. This is not because the conjugate constructed with peptide 5 is a poor immunogen; when administered in additional booster immunizations several weeks after the first immunization, the peptide 5 conjugate induces effective levels of anti-GnRH antibodies (of approximately 12-18 pmole/ml ABC). In this regard, the peptide 5 conjugate behaves similarly to standard GnRH immunogens. However, the conjugate constructed with peptide 5 requires more than one administration, induces lower levels of anti-GnRH antibodies, and takes a longer time to elicit effective antibody levels than do the conjugates of peptides 1-4 of Example 1.
These results also demonstrate the critical contribution of the spacer to the immunogenicity of peptides 1,2,3 and 4 of Example 1. Peptide 5 bears the same immunomimic of GnRH as peptides 1 and 3, yet peptide 5 is inferior as an immunogen. This is because peptide 5 does not contain a spacer sequence, which is present in peptides 1 and 3. Thus, the presence of the spacers in peptides 1,2,3 and 4 of Example 1 makes a critical contribution to their enhanced immunogenicity.
EXAMPLE 4
Conjugates comprising peptides 3 and 4 of Example 1 were mixed 1:1 to give a protein concentration of 2.0 mg/ml in PBS. The mix was then prepared as immunogen and injected into rabbits, as in Example 3. The sera were tested for anti-GnRH antibody by the RIA of Example 3. The results are shown in Table 4 and FIG. 2.
TABLE 4__________________________________________________________________________RABBIT ANTI-GNRH RESPONSES INDUCED BY ONE ADMINISTRATION OF A MIXTURE OF PEPTIDE CONJUGATES ABC (mean ± s.e.) [moles/ml]Day of Test 0 15 24 31 44 59 79 101__________________________________________________________________________ ABC 0 4.6 ± 0.7 21.6 ± 3.3 49.0 ± 9.9 77.8 ± 13.0 86.0 ± 21.0 74.3 ± 22.0 43.0 ± 12.0__________________________________________________________________________
As can be seen from Table 4, effective levels of antibody were induced by the combined administration of the peptide 3 and 4 conjugates. Both peptide components contributed almost equally to the induction of the anti-GnRH antibodies, as shown by antibody specificity testing. The GnRH (1-10)-Arg1 peptide induced antibodies directed predominantly against the carboxy terminal end of GnRH, while the GnRH(1-10)-Arg10 peptide induced antibodies directed against the amino terminal end of GnRH. Thus, conjugates comprising these peptides can be mixed to yield immunogens that induce antibodies against both ends of the target molecule.
EXAMPLE 5
When the peptides of Example 1 are conjugated to DT and prepared as described in Example 1, a proportion of the product is present as a precipitate. The formation of the precipitate is dependent upon various physical parameters, including concentration of conjugate, pH and salt concentration. We prepared a conjugate of peptide 2 of Example 1 to DT as described in Example 1. From this we prepared three fractions of conjugate, based upon solubility. The conjugate was stirred in 0.01 M phosphate buffer pH=7.2 and the insoluble material was collected by centrifugation as Fraction #1. To the soluble material we added NaCl (to 0.5 M) and adjusted the pH to 6.0 with 0.1 M HCl, which yielded additional precipitate that we collected as Fraction #2. The remaining soluble material served as Fraction #3. Each fraction was lyophilized. The percent recoveries (from the 15 mg of starting material) were: Fraction-1, 36%; Fraction-2, 15%; Fraction-3, 27%; lost, 22%.
Each of the fractions 1-3 were injected into a group of mice, at 6 mice/group. (100 μg conjugate/mouse, with 25 μg nMDP, in 0.1 ml of a 1:1 mixture of FTA buffer (containing conjugate+adjuvant) to squalene-arlacel, i.p.). The mice received a single injection of immunogen, after which sera samples were obtained at intervals and tested for anti-GnRH antibody by the RIA of Example 3. The results of this test are shown in Table 5 and in FIG. 3.
TABLE 5__________________________________________________________________________ANTI-GnRH RESPONSES OF MICE TO SOLUBILITY FRACTIONS OF CONJUGATEConjugateABC (mean ± s.e.) [moles/ml]FractionDay 0 Day 14 Day 21 Day 28 Day 36 Day 45 Day 56__________________________________________________________________________1 0 1.7 ± 0.3 4.5 ± 0.4 4.6 ± 0.4 5.6 ± 0.4 5.9 ± 0.5 5.6 ± 0.4 2 0 1.7 ± 0.4 4.2 ± 0.3 4.6 ± 0.2 5.7 ± 0.2 5.8 ± 0.2 5.8 ± 0.2 3 0 1.7 ± 0.3 4.0 ± 0.3 4.5 ± 0.3 5.3 ± 0.3 5.3 ± 0.3 5.0 ± 0.3__________________________________________________________________________
As the results show, each mouse group produced equally potent anti-GnRH antibody responses. This demonstrates that despite variances in the solubility of conjugates produced from the peptide of Example 1, the soluble and insoluble forms can be administered as immunogens and are of equivalent immunogenicity.
EXAMPLE 6
We constructed conjugates of peptides 1 and 2 of Example 1 to DT as described in Example 1. By varying the quantities of reduced peptide added to DT, we constructed conjugates with different peptide:DT substitution ratios. The substitution ratios, determined by amino acid analysis of the conjugates are shown in Table 6:
TABLE 6______________________________________Conjugate Peptide Used Peptide:DT Number (from Example 1) Substitution Ratio______________________________________6.1 1 4.7 6.2 1 13.1 6.3 1 25.9 6.4 2 5.1 6.5 2 12.8 6.6 2 30.1______________________________________
Mice were immunized with each conjugate preparation. The immunization and subsequent assay procedures were identical to those described in Example 5 (6 mice/group). The results of this test are shown in Table 7 and in FIG. 4.
TABLE 7__________________________________________________________________________ANTI-GnRH RESPONSES OF MICE TO PEPTIDE-CARRIER CONJUGATES WITH A DIFFERENT SUBSTITUTION RATIOSPeptide:DT Conjugate Substitution ABC (mean ± s.e.) [pmoles/ml]numberRatio Day 0 Day 14 Day 28 Day 45 Day 56 Day 70 Day 85 Day 105__________________________________________________________________________6.1 4.7 0 0.7 ± 0.1 5.1 ± 0.4 9.8 ± 0.5 9.4 ± 0.4 10.5 ± 0.6 11.0 ± 0.8 10.0 ± 1.0 6.1 13.1 0 1.8 ± 0.3 7.4 ± 0.6 9.7 ± 0.4 10.1 ± 0.2 12.2 ± 0.2 11.9 ± 0.2 11.0 ± 0.2 6.3 25.9 0 0.4 ± 0 2.1 ± 0.5 4.9 ± 1.0 5.1 ± 1.1 4.7 ± 1.3 5.7 ± 1.7 4.7 ± 1.6 6.4 5.1 0 1.7 ± 0.6 4.1 ± 0.6 4.6 ± 0.7 5.0 ± 0.6 6.8 ± 0.9 7.3 ± 1.2 6.7 ± 1.1 6.5 12.8 0 1.4 ± 0.1 4.5 ± 0.2 5.4 ± 0.3 6.1 ± 0.4 7.2 ± 0.2 8.4 ± 0.3 7.9 ± 0.3 6.6 30.1 0 1.1 ± 0.4 3.9 ± 0.4 4.6 ± 0.4 5.4 ± 0.4 6.6 ± 0.5 7.4 ± 0.5 7.0 ± 0.5__________________________________________________________________________
As the results show, significant anti-GnRH responses were induced by each of the conjugate preparations. This demonstrates that the peptides of Example 1 can be conjugated to carriers over a broad range of peptide:carrier substitution ratios and yield effective immunogens.
EXAMPLE 7
We constructed conjugates of peptides 1 and 2 of Example 1 to DT as described in Example 1. The peptide:DT substitution ratio for peptide 1 (GnRH(1-10)-Ser1) was 13.1:1 and the ratio for peptide 2 (GnRH(1-10)-Ser10) was 12.8:1.
We prepared immunogen by emulsifying aqueous phase (containing a mixture of the two conjugates plus norMDP in PBS) with oily vehicle as described in Example 3. The oily vehicle used was Montanide ISA 703 containing 1.8% aluminum monostearate. "Montanide ISA 703 AMS" is manufactured and sold by SEPPIC, Inc. (Paris, France). The final concentrations of the active components in the immunogen were: GnRH (1-10)-Ser1-DT=0.5 mg/ml; GnRH (1-10)-Ser10-DT=0.5 mg/ml; norMDP=0.1 mg/ml. 1.0 ml of immunogen was injected into each of 3 male rabbits, administered to the rear leg muscles (2 sites/rabbit, 0.5 ml/site), on day 0 of the test. Blood was collected from each rabbit prior to immunization and on selected days thereafter. Serum was prepared from each blood sample and stored frozen at -20° C. until utilized in assays to determine the presence of anti-GnRH antibodies (as described in Example 3).
The mean ABC's measured in the sera from these three male rabbits are shown in Table 8 and in FIG. 5. As the results show, a single immunization with the DT conjugates of peptides 1 and 2 of Example 1 in the Montanide ISA 703 containing 1.8% AMS rapidly induced potent antibody responses against GnRH. These anti-GnRH responses are representative of responses induced by the peptide conjugates (individually or mixtures thereof) of this invention when administered with norMDP in an emulsion comprising equal parts aqueous phase and Montanide ISA 703 containing 1.8% AMS.
TABLE 8______________________________________ Mean ABC Day (pmol/ml) (± s.e.) Day Mean ABC (pmol/ml) (± s.e.)______________________________________0 0.02 (± 0.1) 46 543 (± 85.0) 7 0.18 (± 0) 60 1061 (± 368.2) 14 3.71 (± 0.8) 74 1303.3 (± 527.6) 24 40.3 (± 7.7) 88 1320.7 (± 602.9) 32 131.5 (± 29.1) 102 1272 (± 558.1) 40 374.7 (± 13.1) -- --______________________________________
EXAMPLE 8
The production of gonadal steroids can be assessed as a measure of GnRH-immunogen efficacy in immunized animals. We measured testosterone levels in the serum samples obtained from the three male rabbits of Example 7. The testosterone levels were determined using a radioimmunoassay kit for testosterone determination ("Coat-a-Count", purchased from Diagnostic Products Corp., Los Angeles, Calif., USA). The results presented in Table 9 and in FIG. 5 show the immunogen induced levels of anti-GnRH antibodies that totally inhibited the production of testosterone in the male rabbits.
Testosterone was undetectable in the sera of 2 animals by day 24 of the test, and in all 3 rabbits by day 32. The drop in testosterone serum coincides with the rise in anti-GnRH Ab titer, as can be seen in FIG. 5.
TABLE 9______________________________________Testosterone Levels In Immunized Rabbits Day Mean T (ng/ml) (± s.e.) Day Mean T (ng/ml) (± s.e.)______________________________________0 0.32 (± 0.2) 46 0 7 1.37 (± 0.1) 60 0 14 1.21 (± 0.5) 74 0 24 0.1 (± 0) 88 0 32 0 102 0 40 0 -- --______________________________________
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#/note= "immunomimic" - - (xi) SEQUENCE DESCRIPTION: SEQ ID NO:3: - - Xaa His Trp Ser Tyr Gly Leu Arg Pro Gly 1 5 - # 10 - - - - (2) INFORMATION FOR SEQ ID NO:4: - - (i) SEQUENCE CHARACTERISTICS: (A) LENGTH: 6 amino - #acids (B) TYPE: amino acid (D) TOPOLOGY: linear - - (ii) MOLECULE TYPE: peptide - - (iii) HYPOTHETICAL: YES - - (v) FRAGMENT TYPE: C-terminal - - (ix) FEATURE: (A) NAME/KEY: Peptide (B) LOCATION: 1..6 (D) OTHER INFORMATION: - #/note= "spacer" - - (xi) SEQUENCE DESCRIPTION: SEQ ID NO:4: - - Arg Pro Pro Pro Pro Cys 1 5 - - - - (2) INFORMATION FOR SEQ ID NO:5: - - (i) SEQUENCE CHARACTERISTICS: (A) LENGTH: 17 amino - #acids (B) TYPE: amino acid (D) TOPOLOGY: linear - - (ii) MOLECULE TYPE: peptide - - (iii) HYPOTHETICAL: YES - - (ix) FEATURE: (A) NAME/KEY: Region (B) LOCATION: 1..7 (D) OTHER INFORMATION: - #/note= "spacer" - - (ix) FEATURE: (A) NAME/KEY: Region (B) LOCATION: 8..17 (D) OTHER INFORMATION: - #/note= "immunomimic" - - (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: 17 (D) OTHER INFORMATION: - 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- (ii) MOLECULE TYPE: peptide - - (iii) HYPOTHETICAL: YES - - (ix) FEATURE: (A) NAME/KEY: Region (B) LOCATION: 1..6 (D) OTHER INFORMATION: - #/note= "spacer" - - (ix) FEATURE: (A) NAME/KEY: Region (B) LOCATION: 7..16 (D) OTHER INFORMATION: - #/note= "immunomimic" - - (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: 16 (D) OTHER INFORMATION: - #/label= GlyNH2 /note= - #"glycinamide" - - (xi) SEQUENCE DESCRIPTION: SEQ ID NO:7: - - Cys Pro Pro Pro Pro Arg Glu His Trp Ser Ty - #r Gly Leu Arg Pro Xaa 1 5 - # 10 - # 15 - - - - (2) INFORMATION FOR SEQ ID NO:8: - - (i) SEQUENCE CHARACTERISTICS: (A) LENGTH: 10 amino - #acids (B) TYPE: amino acid (D) TOPOLOGY: linear - - (ii) MOLECULE TYPE: peptide - - (iii) HYPOTHETICAL: YES - - (v) FRAGMENT TYPE: C-terminal - - (ix) FEATURE: (A) NAME/KEY: Peptide (B) LOCATION: 1..10 (D) OTHER INFORMATION: - #/note= "immunomimic" - - (ix) FEATURE: (A) NAME/KEY: Modified-sit - #e (B) LOCATION: 10 (D) OTHER INFORMATION: - #/label= GlyNH2 /note= - #"glycinamide" - - (xi) SEQUENCE DESCRIPTION: SEQ ID NO:8: - - Gly His Trp Ser Tyr Gly Leu Arg Pro Xaa 1 5 - # 10 - - - - (2) INFORMATION FOR SEQ ID NO:9: - - (i) SEQUENCE CHARACTERISTICS: (A) LENGTH: 7 amino - #acids (B) TYPE: amino acid (D) TOPOLOGY: linear - - (ii) MOLECULE TYPE: peptide - - (iii) HYPOTHETICAL: YES - - (v) FRAGMENT TYPE: N-terminal - - (ix) FEATURE: (A) NAME/KEY: Peptide (B) LOCATION: 1..7 (D) OTHER INFORMATION: - #/note= "spacer" - - (xi) SEQUENCE DESCRIPTION: SEQ ID NO:9: - - Cys Pro Pro Pro Pro Ser Ser 1 5 - - - - (2) INFORMATION FOR SEQ ID NO:10: - - (i) SEQUENCE CHARACTERISTICS: (A) LENGTH: 7 amino - #acids (B) TYPE: amino acid (D) TOPOLOGY: linear - - (ii) MOLECULE TYPE: peptide - - (iii) HYPOTHETICAL: YES - - (v) FRAGMENT TYPE: C-terminal - - (ix) FEATURE: (A) NAME/KEY: Peptide (B) LOCATION: 1..7 (D) OTHER INFORMATION: - #/note= "spacer" - - (xi) SEQUENCE DESCRIPTION: SEQ ID NO:10: - - Ser Ser Pro Pro Pro Pro Cys 1 5 - - - - (2) INFORMATION FOR SEQ ID NO:11: - - (i) SEQUENCE CHARACTERISTICS: (A) LENGTH: 6 amino - #acids (B) TYPE: amino acid (D) TOPOLOGY: linear - - (ii) MOLECULE TYPE: peptide - - (iii) HYPOTHETICAL: YES - - (v) FRAGMENT TYPE: N-terminal - - (ix) FEATURE: (A) NAME/KEY: Peptide (B) LOCATION: 1..6 (D) OTHER INFORMATION: - #/note= "spacer" - - (xi) SEQUENCE DESCRIPTION: SEQ ID NO:11: - - Cys Pro Pro Pro Pro Arg 1 5__________________________________________________________________________
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Immunogenic compositions capable of generating an immune response in mammals against GnRH are disclosed. The immunogenic compositions are effective in methods of treating gonadotropin and gonadal steroid hormone dependent diseases and immunological contraception of mammals.
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CROSS REFERENCE TO RELATED APPLICATIONS
The present application claims priority to the US provisional application for an “Accelerometer” having application Ser. No. 60/988,114, which was filed on Nov. 15, 2007, which is incorporated herein by reference
BACKGROUND OF INVENTION
The present invention relates to micro-mechanical electrical systems (MEMS) type device for measuring vibration and movement, and more particularly to a MEMS accelerometer.
MEMS type devices for use as sensors and accelerometers are well known. Such devices are generally fabricated on a silicon or related planar substrate by semi-conductor manufacturing type methods, such as the use of photo-resists, masks and various etching processes to fabricate a proximity sensor that includes a suspended proof mass member and means to measure the deflection of the proof mass suspending means. Such devices have inherent limitations on the minimum size, detection limit, sensitivity and the like, largely due to the means used for detecting the deflection of the proof mass.
It is therefore a first object of the present invention to provide 3-dimensional capacitive accelerometer that could be fabricated using a single process.
Yet a further objective is to provide maximum capacitive sensitivity with minimum packaged size of the accelerometer. Obtaining this objective enable a highly efficient accelerometer that provides maximum response with minimum power demands.
It is still a further object of the invention to provide a means to combine multiple accelerometers in a configuration for the simultaneous measurement acceleration in three dimensions.
It is a further objective to provide such a 3-dimensional accelerometer that can be used in cardiovascular applications for example, in a linear structure that is easy for fabrication and packaging in a lead or catheter.
SUMMARY OF INVENTION
In the present invention, the first object is achieved by providing an accelerometer device comprising a substantially planar substrate having an aperture frame therein, one or more static electrodes plates extend into an over the aperture frame from the edge thereof, at least one dynamic electrode plate disposed below said one or more first electrode and supported by at least one torsion beam that spans the aperture, a proof mass coupled to and disposed below said dynamic electrode plate such that the COG (center of gravity) is below the plane of the dynamic electrode, wherein at least one capacitive sensing circuit is defined by the electrical communication between said static electrode plate and said dynamic electrode plate.
A second aspect of the invention is characterized in by the accelerometer for sensing acceleration perpendicular to a substantially planar substrate having at least two aperture frames disposed therein, one or more static electrodes plates extend into and over each aperture frame from the edge thereof, At least one dynamic electrode plate disposed below said one or more static electrode plates associated with each aperture frame, wherein at least one capacitive sensing circuit is defined by the electrical communication between said one or more static electrode plate and said dynamic electrode plates, each dynamic electrode plate comprising, at least one torsion beam portion that spans the aperture frame to suspend each dynamic electrode plate below said one or more static electrode plates associated with the aperture frame, each beam portion being parallel and disposed in the common plane parallel with the plane of said substrate, a proof mass coupled having at least a portion below the upper plan of the substrate, each proof mass is offset from the axis of the associated torsion beam portion; below each dynamic electrode plate such that the COG (center of gravity), and laterally in the opposite directions from another dynamic plate to cancel the their respective capacitive charges induced by acceleration in the plane of the substrate and add the capacitive charges induced by acceleration orthogonal to the plane of the substrate.
Another object of the invention of providing a 3-dimension accelerometer is achieved by combining on a common planar substrate two orthogonal disposed accelerometer devices for measuring acceleration in the plane of the substrate in line adjacent a third accelerometer for sensing acceleration perpendicular to a substantially planar substrate.
The above and other objects, effects, features, and advantages of the present invention will become more apparent from the following description of the embodiments thereof taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-section view of the substrate.
FIG. 2 is a cross-section view of the of FIG. 1 substrate as etched to form a first embodiment.
FIG. 3 is a cross-section view of the substrate of FIG. 2 as etched to form a second embodiment.
FIG. 4A is a plan view of the static electrode layer of an embodiment of a 3-Dimensional accelerometer, which includes the embodiment shown in FIG. 2 as well as that shown in FIG. 3 .
FIG. 4B is a plan view of the dynamic electrode layer of the embodiment of FIG. 4A .
FIG. 5A is a plan view of the Z-axis accelerometer of FIG. 4A .
FIG. 5B is a plan view of a portion of the Z 2 component of the accelerometer in FIG. 5A .
FIG. 6A-C is a schematic diagram illustrating the movement of each of the dynamic electrodes and proof masses in FIG. 4 for X, Y and Z acceleration respectively.
FIG. 7 is an electrical schematic of the capacitive circuit and sensing electronics.
FIG. 8 is a graph of the capacitance changes of the X accelerometer vs. acceleration.
FIG. 9 is a graph of the Capacitive sensitivity of the X accelerometer vs. acceleration.
FIG. 10 is a graph of the capacitance of the Z accelerometer vs. acceleration.
FIG. 11 is a graph of the capacitive sensitivity of the Z accelerometer vs. acceleration.
FIG. 12A is a plan view of an alternative embodiment of the accelerometer of FIG. 3 . whereas FIG. 12B is a cross-section elevation of the same as reference line B-B.
DETAILED DESCRIPTION
Referring to FIGS. 1 through 12 , wherein like reference numerals refer to like components in the various views, there is illustrated therein a new and improved accelerometer, generally denominated 100 herein.
Accelerometers fabricated on semiconductor substrates such as silicon wafers are well known. They frequently deploy one or more static electrodes spaced apart from dynamic electrodes that move in response to acceleration. A silicon substrate from which the structure is fabricated is also etched in some manner to form a spring or hinge that allows the dynamic electrode to move. The change in capacitance between the static and dynamic electrodes, upon movement of the dynamic electrode, is used to quantify the magnitudes and direction of the movement. The dynamic electrode acts as the proof mass that increases its movement in response to the acceleration.
In accordance with the present invention, the accelerometer is preferably a MEMS device fabricated from a double silicon oxide layer substrate shown in FIG. 1 . In this embodiment, double silicon oxide layer substrate 10 is preferably comprised of at least 5 layers. The first or device layer 101 is preferably made out of doped crystalline silicon (Si(c)) that is preferably 10 μm thick and is separated from the second device layer 103 by a buried oxide layer 102 which is about 2.5 μm thick. The second device layer 103 , also is preferably comprised of doped Si(c) and has a thickness of about 15 μm; it is, in turn, separated from the bottom or handle layer 105 by another buried oxide layer 104 (also about 2.5 μm thick). The handle layer is preferably about 680 μm thick and is also preferably comprised of Si(c).
As shown in FIGS. 2 and 3 , the double silicon oxide layer enables a preferred means for device fabrication wherein the static electrode 110 is formed in the first or device silicon layers 101 and a dynamic electrode 120 is formed in the second device layer 103 . As the dashed or broken line indicates an etch boundary, wherein portions of each silicon or silicon oxide layers are partially etched away to define and release the static 110 and dynamic electrodes 120 . Thus, as is illustrated in FIG. 2 and FIG. 3 , the etch boundaries also define the extent of the static and dynamic portions of the device. The upper silicon oxide layer 102 is etched away to release the static upper electrode portion 110 from the lower dynamic electrode 120 . However, only a portion of the handle layer 105 is etched away to provide for a large proof mass portion 122 that is attached to the bottom of the otherwise planar dynamic electrode 120 .
As will be shown in additional embodiments and examples, the first silicon oxide layer 102 is preferably etched away through holes that are formed in the static electrode layer 110 , thus releasing the dynamic electrode 120 , which is connected to the substrate at a spring or beam element 121 formed in the first device layer 101 . Thus, a portion 102 a of the first silicon oxide layer 102 remains to connect this spring or beam element 121 to the dynamic electrode 120 .
Another portion 104 a of the second silicon oxide layer 104 remains to connect the bottom of the dynamic electrode 120 to the proof mass 122 formed in the handle layer 105 . As the proof mass 122 is attached to the back or lower side of the dynamic electrode 120 it is preferably defined by etching the back or handle side of the wafer 122 .
The electrodes of the device 100 are formed within an aperture type frame 109 in a planar substrate, as shown in FIG. 4 . The term aperture frame is intended to indicate the general region that is a least partially etched to define the static and dynamic electrode elements. Thus, the upper or front side of substrate 100 is masked to define the aperture 109 and the full extent of the static and dynamic electrode, while the lower or back side of substrate 100 is masked to define the proof mass 122 dimensions. The etching of a complete open aperture is not necessary, as a portion of the upper silicon layer 101 remains to connect the static electrode 110 mechanically, as well as to provide one or more electrical contacts. However, to the extent that the static electrode contacts the edge of the frame, a trench 115 that extends to the first silicon oxide layer 102 is provided to electrically isolate the electrode from the surrounding silicon layer 101 of substrate 10 on the other side of the aperture frame. Further, in preferred embodiments, such trenches 115 are also used to subdivide the static electrode into two or more regions, labeled with A and B as a suffix to the reference numerals in FIG. 5 , to provide differential capacitive sensing. Thus, the aperture frame 109 represents the linear extension of a plurality of isolation trenches and completely etched regions that collectively electrically isolate the static electrode. It should be appreciated that in the 3-dimensional sensing device of FIG. 4 , all three accelerometer elements used to sense X, Y and Z axis acceleration can be formed within a single frame, or three separate adjacent frames on the same substrate 100 .
In the embodiment in FIG. 2 the proof mass is symmetrically disposed on opposite sides of the torsion beam portion 121 , with the center of gravity of the effective proof mass assembly disposed below the torsion beam axis.
In contrast, in the device 100 of FIG. 3 , the proof mass 122 is offset to the right of the torsion beam axis 121 , and comprises both an upper proof mass 122 a and a lower proof mass 122 b . The upper proof mass 122 a extends through an additional portion of the aperture 109 , or an additional aperture etched in the device layer 101 of substrate 10 . The extension of the proof mass above and below the dynamic electrode 120 increase the magnitude of the mass and further extends the center of gravity away from directly under the torsion beam axis to increase device sensitivity.
As the center of gravity of the proof mass 122 and dynamic electrode 120 combination is below the plane of the dynamic electrode 120 , any acceleration in the plane of the substrate having a component perpendicular to the torsion beam axis 121 a will cause the dynamic electrode to tilt about this axis. Hence the gap between the static and dynamic electrodes will vary from the constant value in the resting state, defined by the thickness of oxide layer 102 . That is, the gap will become smaller at one end of the dynamic electrode extended away from the torsion axis in the direction of the acceleration vector. As the gap at the other end of the dynamic electrode increases, it is desirable to electrically isolate opposing halves of at least one of the dynamic and static electrodes plates to form either a half or full bridge capacitive circuit. This permits differential measurements using the circuit shown in FIG. 7 . Such isolation is provided by trench 115 ′. It should be understood that in the embodiments shown in FIGS. 2 and 3 that the gap between static 110 and dynamic electrodes plates 120 varies with distance from the torsion beam axis 121 a.
It should be appreciated that the holes in the static electrode plate 110 not only permit etching away the first silicon oxide layer 102 , and release of the release dynamic electrode 120 , but also reduce air damping effect by releasing (or admitting) air as the gap between the static and dynamic electrodes decreases (or increases).
It is also preferred to limit the effective capacitive size of the static electrode 110 by using a trench to electrically isolate the sub-region closest to the torsion spring member 121 , as this minimizes the response non-linearly as the gap in this sub-region changes more rapidly being closer to the torsion beam 121 .
Alternatively, the static and dynamic electrodes need not be disposed one above the other as shown in FIGS. 2 and 3 , but can be configured as shown in FIGS. 12A and 12B wherein a substrate 10 with a single buried oxide 102 layer is etched to provide the lower proof mass 122 , but with the static 110 and dynamic 120 electrodes both formed as a plurality of alternating interdigitated fingers in the upper silicon layer such that as the dynamic electrode rotates. As shown in FIG. 12B , the gap between electrodes remains constant, but the projected overlapping area between electrodes decreases, as indicated by the widely hatched regions 1201 a and 1201 b.
FIG. 4A is a plan view showing the substrate 10 with at least one aperture frame 109 supporting an array of static electrodes 110 in three accelerometer devices denoted X, Y and Z for measuring acceleration in the X, Y and Z axis respectively. Conductor traces 130 lead from each accelerometer to a series of terminal pads at the right edge of the device. Broken lines 121 a illustrate the orientation of the torsion beam axis for each accelerometer element. The electrically isolated halves of each static electrode are denoted 110 A and 110 B, each leading to a separate terminal pad at the right side of device 100 . The dynamic electrode 120 of each separate X, Y and X device on substrate is labeled C and is connected to a separate terminal pad thus labeled at the right side of device 100 . Thus for each of the X and Y accelerometer elements there is a set of three terminal pads, grouped by brackets labeled X and Y. FIG. 4B is a section parallel to the view of FIG. 4A to shown the dynamic electrode layout.
FIG. 5A is a more detailed plane view of the Z-axis accelerative sensor having two device Z 1 and Z 2 . Each of Z 1 and Z 2 has the static electrode split into two portions 110 A and 110 B. However, the A portions of static electrodes for Z 1 and Z 2 connect at a common terminal pad A (via metal or conductive traces 130 ) whereas the B portions of static electrode for Z 1 and Z 2 connect at a different common terminal pad each being electrically isolated from the other conductive layers or portion of substrate 10 . The dynamic electrodes of each of Z 1 and Z 2 ; labeled C 1 and C 2 ; are connected to different isolated pads with the same labels.
FIG. 5B illustrates an enlarged portion of the Z accelerometer showing portion of the two static electrodes 110 A and 110 B, two spring elements 121 and the structure 135 around the spring 121 for the purpose of providing electrical isolation between the electrodes of the structure, and it is grounded by a line which is connected to ground pad. The trenches 115 provide electrical insulations between regions with different potential. The conductive lines or traces 130 provide electrical contact between them. An electrical contact or via 127 traverses the buried oxide layer 102 to provide electrical continuity between the square pad 126 a and spring element 121 a that connects the dynamic electrode plate 120 to terminal pad at the edge of the device. The white areas in the figure denote etched areas; therefore there is electrical insulation between each of the regions of the structure. As can be seen from the figure, the static electrode contains many holes (grid pattern) the size of each hole is 3×3 μm. The depth of each hole is 10 μm (thickness of the device layer). The distance between two holes is also 3 μm.
FIG. 5B also illustrates a more detailed view of the torsion structure 121 connecting the dynamic electrode to the substrate at the frame boundary 109 in FIG. 5A . Spring element 121 has two branched portions 124 a and 124 b that span the gap between the aperture 109 and the dynamic electrode 120 . The branch portions 124 a and b each connect via a narrower segment 125 a and b respectively to square pads 126 a and b that holds the proof mass 122 . The beam spring dimensions are 40×3×10 μm 3 .
FIG. 6A-C illustrates the general principle of operation of the 3-D accelerometer of FIG. 4 for the simple case where the acceleration is restricted to a single coordinate axis. Thus each of FIG. 6A-C is an the x-axis elevation of the different dynamic electrode plate and proof mass for each of the X, Y and Z one dimensional accelerometers. It should be appreciated from these diagrams that acceleration in the two orthogonal directions X and Y that are in the plane of the substrate is primarily sensed by the accelerometers 100 of the type shown in FIG. 2 . However, acceleration in the Z direction, orthogonal to the plane of the substrate is sensed by the accelerometer, denoted by bracket Z, that comprises two of the accelerometers of FIG. 2 , denoted Z 1 and Z 2 in the figures.
In FIG. 6A , the relative movement of each dynamic electrode is shown for acceleration in the X-direction, as shown by the bold arrow beside the figure title. However, for the Y-axis sensor the orthogonal elevation of the dynamic electrode and proof mass is also shown just below the x-axis elevation. The torsion axis of each dynamic electrode, when viewed in section, is denoted by an upright triangle. The dashed lines show the equilibrium position of each dynamic electrode. Thus in FIG. 6A , the X-dynamic electrode to the right tilts, but the Y-dynamic electrode is stable. However, as the Z 1 and Z 2 dynamic electrodes have their center of masses on opposite sides they tilt in the same direction, the right side tilting up and the left side tilting down. It should be appreciated that and since the A and B electrode pairs are constituted from opposite sides of the Z 1 and Z 2 device, this movement in the same direction will create an equal and opposite change in capacitance for the combined electrodes so that the net change will be null.
In FIG. 6B , the relative movement of each dynamic electrode is shown for acceleration in the Y-direction, as shown by the letter “X” beside the figure title to indicate the acceleration is into the plane of the paper. However, only the Y-dynamic electrode tilts.
In FIG. 6C , the relative movement of each dynamic electrode is shown for acceleration in the Z-direction, as shown by the bold arrow beside the figure title. The X and Y dynamic electrodes do not tilt, as the proof mass has a center of gravity directly below the torsion axis. However, as the proof mass in each of the Z 1 and Z 2 dynamic electrodes is offset in a different direction laterally from the torsion axis, each electrode plates now tilts in opposite directions, forming an “x” shape profile. Now, the A and B electrodes pairs reinforce each other to increase the capacitance reading, rather than cancelling.
While it is preferred for some application that each of accelerometer be placed adjacent to each other in a row to form a device with a 3:1 aspect ratio, such as for placement in narrow catheter leads, other arrangements and combinations may be desired in different applications.
Preferably, the two Z-axis one dimensional accelerometer devices are co-planar with at least one of the X- and Y-one dimensional accelerometer devices, that is with the static electrode plates and torsion beam axis of all devices in a common plane. While the torsion beam component could be a single rod that extends entirely across the dynamic electrode, preferably the torsion beams have two co-linear segments that extend from the frame edge on to the second electrode.
The capacitive sensitivity was calculated by finite element methods (FEM) taking into account the grid structure of the top electrodes to account for the reduction in air damping due to the hole in the upper or static electrode plate.
The size of each hole in the electrode is 3×3 μm and the distance between two adjacent holes is also 3 μm. The gap between the static electrode and dynamic electrodes is 2.5 μm (the thickness of the buried oxide layer).
The static capacitance between moving and static electrodes was calculated at the equilibrium state. This required the calculation and accounting for the distribution of electric potential within the unit cell element of the electrode structure: The unit cell element for modeling purposes consisted of a segment of the moving electrode with a size of 6×6 μm (shown at the bottom of the figure) and a segment of the static electrode with a size of 6×6×0 μm 3 . The following boundary conditions were used in the calculations: 1) Bottom face of the structure corresponding to the moving electrode is grounded, 2) All facets corresponding to the static electrodes have potential V and all other facets have symmetry boundary conditions.
The capacitance was calculated from the formula:
W
ς
=
1
2
ς
V
2
Where Wc the electric energy of the capacitor and C is the capacitance
The simulations surprisingly showed that the resulting capacitance is only on a factor K=0.9738 which is smaller than the capacitance of the equivalent capacitor without the hole i.e. due to the grid pattern (and its hole structure) we lose only 2.62% from the capacitance. The air velocity within the unit cell due to the movement of the dynamic electrode was also considered in the model to calculate the therm-mechanical noise of the structure that arises from the air damping that results from the movement of the proof mass.
From the distribution of the air velocity resulting from the movement of the bottom of the moving electrodes in the Z direction the damping in the unit cell was calculated as the integral of the force that is applied against the direction of the motion. The resulting damping coefficient is:
D
=
D
ς
·
A
36
Where D 0 =910 −8 kg/sec and A is the area of the electrode in μm 2 .
In each of the one dimensional accelerometers the sense capacitance between two electrodes (A and C for example) increases when the sense capacitance between the other electrodes (B and C for example) decreases by the same amount. These two sense capacitors are connected to create a half-bridge capacitor circuit of FIG. 7 . The signal from a crystal oscillator with amplitude Vo is applied to the static electrodes A and B. The sense signal is read from the electrode in the proof mass (electrode C). This signal is then amplified by the pre-amplifier of an ASIC.
Following this, the signal is mixed with the original signal and following a low pass filter to obtain the output signal (V out ).
The FEM model was extended for the X and Y accelerometers of the type shown in FIG. 2 , to calculate the change of the capacitance vs. the acceleration. FIG. 8 shows the calculated change in capacitance of the X or Y type accelerometer vs. acceleration for each pair of electrodes as well as the differential signal accelerometer. At the equilibrium the sense capacitance is about 0.5 pF. While the capacitance of the first electrode increases, the capacitance of the other sensing electrode decreases. This total change of the capacitance is also shown.
Further, as shown in FIG. 9 the capacitive sensitivity of the X, Y accelerometer was calculated vs. acceleration. The graph above shows the change of the capacitance sensitivity of the X (Y) accelerometer versus the acceleration. The total capacitance sensitivity is the difference of the capacitive sensitivities of the two sensing electrodes and is represented by the solid line. As we can see, the capacitance sensitivity at the equilibrium is about 31 pF/g.
FIGS. 10 and 11 shows the results of the corresponding calculations for the Z axis accelerometer, we calculated the change of the capacitance vs. the acceleration. At the equilibrium the sense capacitance is about 0.77 pF. Likewise, while the capacitance of the first electrode increases, the capacitance of the other sensing electrode decreases. As shown in FIG. 11 , the capacitance sensitivity of the Z-axis accelerometer at the equilibrium is about 45 fF/g.
The Table below summarizes the parameters for the specific embodiments of the X, Y and Z accelerometers described above
Parameter
Values
Units
Sensitivity (X, Y, Z)
30.6, 30.6, 44.7
fF/g
Sensing Electrode Capacitance (X, Y, Z)
0.502, 0.502, 0.774
pF
Parasitic Capacitance From MEMS
<1
pF
Resonance Frequency (X, Y, Z)
1.55, 1.55, 1.35
kHz
Nonlinearity
2
%
Thermo-Mechanical Noise Floor (X, Y, Z)
4.15, 4.15, 9.1
μg/√Hz
Q-Factor (X, Y, Z)
1.52, 1.52, 0.5
Capacitance Offset
±5
%
While the invention has been described in connection with a preferred embodiment, it is not intended to limit the scope of the invention to the particular form set forth, but on the contrary, it is intended to cover such alternatives, modifications, and equivalents as may be within the spirit and scope of the invention as defined by the appended claims.
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A 3-dimensional MEMS accelerometer fabricated on a single planar substrate deploys three co-planar sensor elements. Each sensor element is a capacitive device deploying a static electrode plate and a parallel dynamic electrode plate supported by a torsion beam. The dynamic electrode plate also includes a proof mass portion that displaces the center of gravity to below the plane of the plate. Two of the sensor elements are identical and rotated by 90 degrees on the planar substrate. The third capacitive sensor has two pairs of adjacent capacitive plates, each one having a dynamic electrode plate is suspended by a torsion beam. The proof mass on each dynamic electrode plates however is offset laterally from the torsion axis in opposite directions from the other plates to cancel the their respective capacitance charges induced by in-plane acceleration. However, this arrangement also adds the capacitive change induced by acceleration orthogonal to the planar substrate.
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CROSS-REFERENCE TO RELATED APPLICATION APPLICATIONS
This application is a U.S. national phase application filed under 35 U.S.C. §371 of International Application PCT/US2013/029578, filed Mar. 7, 2013, designating the United States, which claims the benefit of U.S. Patent Appl. No. 61/608,080, filed Mar. 7, 2012, which are hereby incorporated by reference in their entirety.
FIELD
Systems and methods for sealing food product containers are described herein, and in particular, systems and methods for sealing food product containers having non-planar flanges.
BACKGROUND
Food product trays typically have planar or flat, symmetric seal flanges. Traditional sealing methods utilise a sealing surface that is applied in one plane that is immediately above the planar surface of the seal flanges. In addition, such methods typically utilize an equal length of lid film stock for a given length of the seal flange of the container such that the seal flange length is equal to its projected dimension on the original, unformed sheet.
The above described methods would not be effective to seal packages having flanges that do not lie in one plane, such as curved or non-planar flanges. For example, in a package with one or more curved flanges, the traditional methods of measuring and applying the lid film would not be feasible because the projected dimension of the seal flange would be less than the length along the curve of the sealing flange and a greater length of lid material would be needed for a corresponding length of the base package. In a package where a portion of the flange curves or otherwise deviates out of the flat plane, traditional methods would result in the curved flange remaining unsealed because the sealing surface would only applied in one plane and would not contact the curved portion of the seal flange.
A method of sealing a package containing a food product is provided. The method comprises applying a lid to a non-planar flange surrounding a periphery of the food package. The method comprises supporting at least a portion of the non-planar flange and progressively sealing the lid to the supported portion of the non-planar flange by applying pressure at one or more tangent points against the lid and the flange using a sealing member having a pressure applying surface that rotates about an axis of rotation and one of radially varies relative to the axis of rotation and the axis of rotation reciprocates.
The step of supporting at least a portion of the non-planar flange can further include supporting the flange along its entire surface during the step of progressively sealing the lid.
The step of supporting at least a portion of the non-linear flange can further include supporting the flange using a flange support surface that rotates about an axis of rotation. The axis of rotation of the flange support surface can be parallel to the axis of rotation of the pressure applying surface.
The non-planar flange can advance in a linear direction perpendicular to the axis of rotation of the pressure applying surface.
The non-planar flange can have a projected length in a machine direction of less than a length along she flange in the machine direction.
The method can further a step of tacking a portion of the lid to a leading end of the non-planar flange.
The method can include sealing a portion of the lid to a leading end of the flange in a first plane and sealing another portion of the lid to a trailing end of the flange in a second plane.
The method of can further include a step of transporting the package along a conveyor surface with a portion of the lid attached to the non-planar flange and a portion of the lid unattached to the non-planar flange.
The method can further include providing a plurality of at least one seat including a cavity configured to receive the package with the flange being at least in part outside of the cavity.
The method can further include a step of providing at least one cylindrical top sealing member having at least one sealing surface configured to rotate and contact the non-planar flange to seal the lid to the package.
The method can also include providing two cylindrical top sealing members where one of the sealing members seals one portion of the lid to one portion of the non-planar flange and the other of the sealing members seals another portion of the lid to another portion of the non-planar flange. The method can further include rotating the two cylindrical sealing members at different speeds.
The method can also include a step of providing a bottom rotary die having a plurality of seats, each seat having a plurality of support surfaces configured to support the non-planar flange, and a top rotary sealing member having a plurality of sealing surfaces configured to rotate and contact the support surfaces of the seats to seal the lid to the package.
The method can also include a step of providing a conveyor surface including a plurality of seats, each seat having a plurality of support surfaces configured to support the non-planar flange, and a top rotary sealing member having a plurality of sealing surfaces configured to rotate over and contact each of the support surfaces to seal the lid to the package.
The method can further include applying the lid onto the flange using a pick and place device including a vacuum.
The method can further include a step of providing the sealing member having the sealing surface that is entirely non-planar.
The method can further include a step of applying the lid onto the flange from a supply film roll using a plurality of rollers, at least one of the rollers including a cutting surface.
The method can further include placing and sealing the lid onto the non-planar flange at one station.
The method can further include creating a pressure atmosphere in the package that urges the lid in a direction away from the food product stored in the package.
The method can also include creating a protective atmosphere in the food package to increase a shell life of the food product stored in the package.
The lid can be made of a flexible film or can be made of a rigid material, such as a suitably rigid blow-molded, injection molded or thermoformed plastic.
The method can further comprise providing a food storage package having a non-planar flange. The package can have a top surface that is entirely non-planar. The package can alternatively have a bottom surface that is in part planar and in part non-planar. The package can include a tray having a non-planar flange.
The method can include a step of using the sealing member having a sealing surface that radially varies relative to the axis of rotation.
The method can include a step of using the sealing member having an axis of rotation that reciprocates.
A package including a non-planar flange made according to any one of aforementioned methods is also provided. The package can include a tray having a non-planar flange.
An apparatus for sealing a lid to a non-planar flange surrounding a periphery of a package containing a food product is provided. The apparatus includes a conveyor surface configured to advance the package. The apparatus further includes a bottom rotary die protruding at least in part above the conveyor surface and having a plurality of seats, each seat having a plurality of support surfaces configured to support at least a portion of the non-planar flange. The apparatus also includes at least one top sealing member having at least one sealing surface configured to rotate and contact the non-planar flange to seal the lid to the flange.
The at least one top sealing member can rotate about a reciprocating axis of rotation to seal the lid to an entire surface of the flange.
The at least one top sealing member can comprise two top sealing members each configured to rotate about a reciprocating axis of rotation to seal the lid to the flange.
The at least one top sealing member can include a first top sealing member configured to seal one portion of the lid to one portion of the flange and a second top sealing member configured to seal another portion of the lid to another portion of the flange.
The top sealing member can comprise a plurality of sealing surfaces and is configured to rotate about one axis of rotation and contact each of the support surfaces of the seats to seal the lid to the package.
Another apparatus for sealing a lid to a non-planar flange surrounding a periphery of a package containing a food product is also provided. The apparatus comprises a conveyor configured to advance the package. The conveyor includes a plurality of seats formed thereon having a plurality of support surfaces configured to support the non-planar flange. The apparatus further includes at least one top sealing member having at least one sealing surface configured to rotate and press the lid against the flange.
The top sealing member can comprise a plurality of sealing surfaces and is configured to rotate about one axis of rotation and contact each of the support surfaces of the seats to seal the lid to the package.
The at least one sealing surface can be non-planar. The at least one sealing surface can be made of a resilient material.
The apparatus can further comprise a device configured to transfer the lid from a supply source and apply the lid onto the flange of the package. The device can comprise a vacuum source configured to lift and move the package.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a perspective view of a first exemplary container having one or more non-planar flanges shown without a lid;
FIG. 2 is a perspective view of the container of FIG. 2 shown with a food product in the hollow interior of the container;
FIG. 3 is the container of FIG. 1 shown sealed with a lid;
FIG. 4 is a side elevational view of the container of FIG. 1 ;
FIG. 5 is a perspective view of a second exemplary container having one or more non-planar flanges shown without a lid;
FIG. 6 is a perspective view of the container of FIG. 5 shown with a food product in the hollow interior of the container;
FIG. 7 is the container of FIG. 5 shown sealed with a lid;
FIG. 8 is a side elevational view of the container of FIG. 5 ;
FIG. 9 is a front elevational view of the sealed container of FIG. 7 , shown being positioned in a vertical orientation;
FIG. 10 is a perspective view of a first exemplary conveyor system for sealing the container of FIG. 1 ;
FIG. 11 is a perspective enlarged fragmentary view of the conveyor system of FIG. 10 , showing the tacking station for tacking a lid to the leading seal flange of the containers;
FIG. 12 is a side elevational view of the tacking station of FIG. 11 ;
FIG. 13 is a top plan view of the conveyor system of FIG. 10 ;
FIG. 14 is a side elevational view of the conveyor system of FIG. 10 ;
FIG. 15 a front perspective enlarged fragmentary view of the conveyor system of FIG. 10 , showing the sealing station for sealing a lid to the seal flanges of the containers;
FIG. 16 a rear perspective enlarged fragmentary view of the conveyor system of FIG. 10 , showing the sealing station for sealing a lid to the seal flanges of the containers;
FIG. 17 is a perspective view of a second exemplary conveyor system for sealing the container of FIG. 1 ;
FIG. 18 is a top plan view of the conveyor system of FIG. 17 ;
FIG. 19 is a side elevational view of the conveyor system Of FIG. 17 ;
FIG. 20 is a side perspective enlarged fragmentary view of the conveyor system of FIG. 17 , showing the mating of the top and bottom rotary sealing members of the sealing station to seal the lid to the leading seal flange of the container of FIG. 1 ;
FIG. 21 is a side perspective enlarged fragmentary view of the conveyor system of FIG. 17 , showing the mating of the top sealing member and the bottom rotary die of the sealing station to seal the lid to the trailing seal flange of the container of FIG. 1 ;
FIG. 22 is a front perspective enlarged fragmentary view of the conveyor system of FIG. 17 , showing the top sealing member and the bottom rotary die of the sealing station separated and the lid fully sealed to the seal flanges of the container of FIG. 1 ;
FIG. 23 is a perspective view of a third exemplary conveyor system for sealing the container of FIG. 1 ;
FIG. 24 is a top plan view of the conveyor system of FIG. 23 ;
FIG. 25 is a side elevational view of the conveyor system of FIG. 23 ;
FIG. 26 is a perspective fragmentary view of the conveyor system of FIG. 23 , showing the mating of the top sealing member and the die train of the conveyor;
FIG. 27 is a front perspective enlarged fragmentary view of the conveyor system of FIG. 23 , showing the mating of the top rotary sealing member and the seat of the die train to seal the lid to the leading seal flange of the container of FIG. 1 ; and
FIG. 28 is a rear perspective enlarged fragmentary view of the conveyor system of FIG. 23 , showing the mating of the top rotary sealing member and the seat of the die train to seal she lid to the trailing seal flange of the container of FIG. 1 .
DETAILED DESCRIPTION
A system and method for sealing of packages having one or more curved, non-planar sealing flanges are provided. The method includes advancing the package having a non-planar seal flange on a conveyor belt in a machine direction. An optional tacking station is located upstream of the sealing station on the conveyor. The tacking station can include a lid material supply roller and plurality of rollers and/or dies which transfer the lid material from the supply roller, out the lid material, tack the lid material to the leading seal flange of the package, and align the lid material over the other seal flanges. The package, with the lid material being tacked to the leading seal flange, can be advanced along the conveyor to a sealing station.
The method also includes creating a single point of contact, or nip point, and allowing the lid material to coincide with and follow the non-planar length of the package instead of the projected length of the seal flange to seal the lid material to the seal flanges. This can be accomplished by utilizing one or more rotary sealing members. The method further can include moving a rotary top sealing member and the package in coordination so as to keep a sealing force constantly perpendicular to the tangent of contact. The system and method will be discussed in greater detail herein following a description of exemplary packages.
With reference to FIGS. 1-4 , an exemplary container 100 having non-planar seal flanges is provided. The term non-planar flange will be understood to mean a flange having a first surface in one plane and a second surface in a different plane. The non-planar flange could be entirely curved, could be curved in part and straight in part, or could have two or more straight portions that are angled relative to one another.
The container 100 can be used to store a food product 130 as shown in FIG. 2 . The food product 130 can be crackers, cookies, wafers, chocolates, candy, or the like. The food product 130 can be stored in one or more stacks or rows as shown in FIG. 2 , or may be dump-filled into the container 100 . The container 100 can be made of a flexible material including, but not limited to polyethylene, polypropylene, or the like. For example, the container 100 can be thermoformed, injection-molded, blow-molded, or the like. The container 100 can also be laminated and optionally include a metalized layer. A lid 134 may be sealed to the container 100 as shown in FIG. 3 to provide the container 100 with a hermetic seal. The lid 134 can be flexible or rigid.
With reference to FIGS. 1 and 4 , the exemplary container 100 can have a bottom wall 116 , a front wall 117 , two opposed side walls 118 and 120 , and a hollow interior 119 therebetween. The container has a leading end 110 (in the machine downstream direction), a trailing end 111 opposite the leading end 110 , a bottom surface 112 , and a top surface 114 opposite the bottom surface 112 . The container 100 does not have a rear wall opposite the front wall 117 . Instead, the container 100 has an open area at the trailing end 111 . This open area can be used to unload the food product 130 stored in the hollow interior 119 of the container 100 onto a serving surface such as a tray or a plate. Optionally, a rear wall opposite the front wall 117 could be provided.
The container 100 includes a leading seal flange 102 , a trailing seal flange 104 , and side seal flanges 106 and 108 . The leading flange 102 and adjacent portions of the side flanges 106 and 108 are flat and lie in the same horizontal plane, together defining the top surface 114 of the container 100 . Portions of the side seal flanges 106 and 108 can curve or deviate in a straight line or otherwise downward from the top surface 114 toward the trailing seal flange 104 . As such, the leading flange 102 and the trailing flange 104 lie in different planes as shown in FIG. 1 . Indeed, the different planes including the leading and trailing seal flanges 102 and 104 are angled relative to each other as can be seen in FIG. 4 . Similarly, the trailing flange 104 and portions of the side flanges 106 and 108 also lie in different planes. The non-planar shape of the sealing flanges of the container 100 provides the container 100 with a distinctive and aesthetically pleasing appearance.
With reference to FIG. 4 , a portion of the leading end 110 of the container 100 can be straight and perpendicular to the top surface 114 . The leading seal flange 102 protrudes beyond and overhangs the leasing end 110 . A curved transition 113 is formed between the leading end 110 and the bottom surface 112 of the container 100 . The portion of the bottom surface 112 proximate the curved transition 113 can be planar or flat and can be parallel to the top surface 114 . The flat portion of the bottom surface 112 of the container 100 allows the container 100 to be stable when positioned on a flat surface such as a shelf or a table.
Proximate the trailing end 111 of the container 100 , the bottom surface 112 of the container 100 can curve or linearly deviate upward to form a raised portion 115 . This non-planar shape of the bottom surface 112 does not undermine the stability of the container 100 when positioned on a flat surface such as a shelf because a majority of the bottom surface 112 is flat. The raised portion 115 can act as stop for the circular food product 130 stored in the hollow interior 119 of the container 100 , and can prevent she food product 130 from inadvertently rolling out of the container 100 .
With continuing reference to FIG. 4 , the non-planar portions of the side flanges 106 and 108 define the trailing end 111 of the container 100 . The trailing end 111 can be curved in part or in its entirety. The trailing end 111 of the container 100 terminates in the trailing seal flange 104 , which extends slightly below the raised portion 115 of the bottom surface 112 of the container 100 .
FIGS. 5-9 illustrate a second exemplary container 200 having one or more non-planar seal flanges. Similar to the container 100 , the container 200 can be used to store a food product 230 , as shown in FIG. 6 . The container 100 can be made of a flexible material including, but not limited to polyethylene, polypropylene, or the like. The container 200 can be laminated and optionally include a metalized layer. For example, the container 200 can be thermoformed, injection-molded, blow-molded, or the like. A lid 234 may be sealed to the container 200 as shown in FIG. 6 to provide the container 200 with a hermetic seal. The lid 234 can be flexible or rigid.
With reference to FIGS. 5 and 8 , the container 200 can have a bottom wall 216 , a front wall 217 , two opposed side walls 218 and 220 , and a hollow interior 219 therebetween. The container 200 also includes a leading seal flange 202 , a trailing seal flange 204 , and side seal flanges 206 and 208 . The leading seal flange 202 can include a tab portion 222 which facilitates the user in peeling off or otherwise removing the lid 234 when opening the container 200 .
Similar to container 100 the container 200 does not have a rear wall opposite the front wall 217 . Instead, the container 200 has an open area between the seal flanges 202 , 204 , 206 , and 208 . This open area can be used to load and/or unload the food product 230 into and out of the container 200 . Optionally, a rear wall opposite the front wall 217 can be provided. The hollow interior 219 of the container 200 can store the food product 230 in one stack as shown in FIG. 6 , or can store a loose food product that can be dump-filled, for example, candy, chips, nuts, or raisins.
With reference to FIG. 8 , the container 200 has a leading end 210 (in the machine downstream direction), a trailing end 211 opposite the leading end 210 , a bottom surface 212 , and a top surface 214 opposite the bottom surface 212 . The leading seal flange 202 can protrude beyond and overhang the leading end 210 of the container 200 . The trailing end 211 of the container 200 terminates in a trailing flange 204 .
With reference to FIG. 8 , the bottom surface 212 of the container 200 proximate the trailing end 211 can curve or deviate in a straight line or otherwise upward to form a raised portion 215 . The trailing seal flange 204 can extend slightly beyond and overhang the raised portion 215 of the bottom surface 212 . The non-planar shape of the bottom surface 212 does not undermine the stability of the container 200 when positioned on a flat surface. Instead, the protruding trailing seal flange 204 and the non-planar shape of the bottom surface 212 can create a point of stability for the container 200 when positioned on a flat surface such as a shelf or table. In addition, the raised portion 215 of the bottom surface 212 can create a stop for the circular food product 230 and can restrict the food product 230 from inadvertently rolling out of the container 200 .
The side flanges 206 and 208 of the container 200 can be non-planar in part or in their entirety from the leading seal flange 202 to the trailing seal flange 204 . As such, the top surface 214 of the container 200 can be non-planar in part or in its entirety. Similarly, the bottom surface 212 of the container 200 can be non-planar in part or in its entirety from the leading seal flange 202 to the trailing seal flange 204 . As such, the container 200 can have a non-planar leading end 210 and a non-planar trailing end 211 . The non-planar shapes of the side flanges 206 and 208 and of the bottom and top surfaces 212 and 214 provide the container 200 with a distinctive and aesthetically appealing appearance.
The container 200 can also be positioned a standing orientation, as shown in FIG. 9 . The non-planar shape of the side flange 206 and the exterior surface of the side wall 213 can create one or more points of stability for the container 200 on a flat surface. The lid 234 may include branding information that is oriented vertically (i.e., going from left to right in the direction from the trailing seal flange 204 to the leading seal flange 202 ) so that the container 200 can foe offered for sale on store shelves in the distinctive standing orientation.
With reference to FIGS. 10-16 , a conveyor system 300 and method of applying and sealing a lid to the container 100 will now be described. It will be appreciated that this and any of the systems and methods described below can be advantageously used to seal the aforementioned container 200 , or any other container having one or more non-planar seal flanges.
FIG. 10 illustrates a conveyor system 300 advancing a plurality of food storage containers 100 in the machine direction indicated by an arrow. The conveyor system 300 includes a tacking station 330 and a sealing station 370 . Generally, as a container 100 passes through the tacking station 330 , a lid or cover is placed onto the container 100 , and when the container 100 passes through the sealing station 370 , the lid is sealed to the seal flanges 102 , 104 , 106 , and 108 of the container 100 to provide a cover and hermetic seal for a food product stored in the container 100 .
With reference to FIGS. 10-12 , the tacking station 330 includes a supply roller 332 which includes the lid material 334 . The lid material 334 can be made from a thin, flexible material, such as a polymer film or laminate, foil, or the like. Alternatively, the lid material 334 can be made from a more rigid material. The lid material 334 can be unwound from the supply roller 332 in the machine direction as a continuous web 335 and is fed via a series of intermediate rollers 338 , 340 , 342 , 344 , and 346 in between a die roller 348 and a vacuum roller 350 . The die roller 348 may include a cutting surface which may be indexed relative to the rotation speed of the die roller 348 such that a piece of lid material 334 of appropriate length to cover the seal flanges 102 , 104 , 106 , and 108 of the container 100 may be cut off from the continuous web 335 by the combined action of the action of the die roller 348 and the vacuum roller 350 .
The vacuum roller 350 has an axis of rotation that can be parallel to the axis of rotation of the supply roller 332 . The axis of rotation of the vacuum roller 350 can also be parallel to the conveyor surface 312 on which the containers 100 travel. The vacuum roller 350 can rotate in a direction opposite to the machine direction. In support member having a plurality of elongate arms 352 rotates beneath the conveyor surface 312 in the machine direction. As the support member rotates, the support arms 352 extend above the conveyor surface 312 as shown in FIGS. 11 and 12 .
As a container 100 moves in the machine direction along the conveyor surface 312 , the vacuum roller 350 applies the lid material 334 onto the leading seal flange 102 of the container 100 . As the lid material 334 is being applied by the vacuum roller 350 to the leading seal flange 102 of the container 100 , the support arm 352 rotates into a position where the support arm 352 is substantially perpendicular to the leading seal flange 102 , as shown in FIG. 11 . In this position, the support arm 352 may be in contact with the underside of the leading seal flange 102 , or may be slightly below the underside of the leading seal flange 102 . The leading flange 102 gets tacked or nipped between the bottom surface of the vacuum roller 350 and the upper surface of the support arm 352 as shown in FIG. 11 . Since the container 100 and the leading flange 102 are flexible, the support arm 352 ensures that the leading seal flange 102 does not bend or break when a sealing force is applied to the leading flange 102 by the vacuum roller 350 .
After the vacuum roller 350 applies the lid material 334 to the leading seal flange 102 of the container 100 , the container 100 moves further in the machine direction along the conveyor surface 312 such that side seal flanges 105 and 108 of the container 100 pass under the vacuum roller 350 . Since portions of the side flanges 106 and 108 are in the same plane as the leading flange 102 , the roller 350 can align the lid material 334 to the side flanges 106 and 108 as shown in FIG. 12 .
During the application of the lid material 334 to the side seal flanges 106 and 108 , the container 100 moves forward and the support arm 352 rotates forward such that the support arm 352 can be maintained in contact with the leading end 110 of the container 100 . The support arm 352 can thus act as a back stop for the container 100 as the lid material 334 is being applied to the side flanges 106 and 108 by the vacuum roller 350 to restrict the container 100 from being inadvertently moved out of position due to the force being applied by the vacuum roller 350 . Since the trailing flange 104 of the container 100 is non-planar and extends below the plane where the leading seal flange 102 lies, the bottom surface of the vacuum roller 350 does not contact the trailing seal flange 104 and the lid material 334 remains unattached to the trailing seal flange 104 when the container 100 exits from the tacking station 330 , as shown in FIG. 12 .
Either or both the underside of the lid material 334 and the upper surface of the leading flange may have an adhesive layer. As such, when the container 100 exits the tacking station 330 , the lid material 334 can be partially attached by an adhesive to the leading seal flange 102 and/or the side seal flanges 106 and 108 . Thus, although the lid material 334 is not attached to the trailing seal flange 104 and not fully sealed to any of seal flanges 102 , 106 , or 108 , the lid material 334 does not shift or fail off the container 100 as the container 100 moves along the conveyor surface 312 toward the sealing station 370 .
It is to be appreciated that instead of the tacking station 330 shown in FIG. 1 , the conveyor system 300 may include a tacking station with a pick and place device. For example, the tacking station would include a stack of pre-cut sheets of flexible lid material 334 or sheets or stacks of rigid lid material 334 sized and shaped to match the size and shape of the seal flanges 102 , 104 , 106 , and 108 of the container 100 . The tacking station would further include a pick and place device which could pick a sheet of lid material 334 off the stack and transfer the sheet of lid material 334 onto a container 100 moving along the conveyor surface 312 . For example, the pick and place device could be vacuum-based and could have one or more points of contact with the lid material 334 . The pick and place device could apply a pressure to the top of the leading seal flange 102 similar to the vacuum roller 350 such that the sheet of lid material 334 placed onto the container 100 by the pick and place device would be tacked to at least the leading seal flange 102 to ensure that the lid material 334 does not inadvertently fail off the container 100 as the container 100 moves along the conveyor surface from the tacking station to the sealing station 370 .
It is to be appreciated that a tacking station such as the tacking station 330 can foe eliminated altogether and flexible or rigid lid material 334 can be transferred from a supply roll or supply stack directly onto the containers and sealed to the seal flanges of the containers 100 in one step at the sealing station 370 . In this approach, the containers 100 having partially attached lid material 334 would not travel along the conveyor surface 312 between the tacking station 330 and the sealing station 370 . Instead, open containers 100 having no lid material 334 applied to them would travel along the conveyor surface 312 until they reach the sealing station 370 , where the lid material 334 would foe applied to the containers 100 for the first time and the containers 100 would be sealed.
With reference to FIG. 10 , at the sealing station 370 , the conveyor surface 312 has a gap and a portion of a bottom rotary die 360 rotates in the gap and protrudes above the conveyor surface 312 . Two top rotating dies or sealing members 366 and 368 rotate over the bottom rotary die 360 . The bottom rotary die 360 can have a fixed axis of rotation and rotates in the machine direction. The bottom rotary die 360 includes a plurality of die seats 362 . Each die seat 362 includes a cavity sized and shaped to receive the containers 100 . Each die seat 362 also includes a plurality of support surfaces 363 , 365 , 367 , and 369 configured to oaten the shape and orientation of the leading, trailing, and side seal flanges 102 , 104 , 106 , and 108 of the container 100 .
As the containers 100 move in the machine direction down the conveyor surface 312 , a portion of the container 100 passes a trailing edge 314 of a section of the conveyor surface 312 and the container 100 is deposited into the cavity of a die seat 362 of the bottom rotary die 360 as shown in FIG. 15 . The container 100 may either be deposited into the die seat 362 of the bottom die 360 solely due to the forward motion of the conveyor surface 312 , or may be assisted by a push from behind by one of the raised ribs 313 , which can be positioned along the conveyor surface 312 at equal or son-equal intervals.
The container 100 is positioned in the die seat 362 such that only the seal flanges 102 , 104 , 106 , and 108 protrude from the cavity formed in the die seat 362 . In particular, the seal flanges 102 , 104 , 106 and 108 of the container 100 rest on the support surfaces 363 , 365 , 367 , and 369 , respectively, of the die seat 362 . As shown in FIGS. 15 and 16 , a rubber or plastic insert 364 may surround the support surfaces 363 , 365 , 367 , and 369 of each seat 362 to compensate for variations in material and machine orientations.
The top rotating sealing members 366 and 368 can be cylindrical and can each have an axis of rotation parallel to the axis of rotation of the bottom rotary die 360 . The first top die 366 has a surface configuration such that the width of the die surfaces 366 a and 366 b protruding from the top die 366 generally match the widths of the side seal flanges 106 and 108 , respectively, of the container 100 . The second top die 368 has a surface configuration such that the width of the die surface 368 a protruding from the die 368 generally matches the widths of the leading and trailing seal flanges 102 and 104 of the container 100 . Optionally, instead of the cylindrical sealing member 366 having sealing surfaces 366 a and 366 b that seal the lid material 334 to the side seal flanges 106 and 108 and the cylindrical sealing member 368 having a sealing surface 368 a that seals the lid material 334 to the leading and trailing flanges 102 and 104 , the conveyor system 300 can include a single top die or sealing member having one or more sealing surfaces configured to seal each of the leading, trailing, and side flanges 102 , 104 , 106 , and 108 of the container 100 .
As such, when a container 100 received in a seat 362 of the bottom rotary die 360 passes under first top die 366 , the top die 366 seals the lid material 334 to the side flanges 106 and 108 of the container 100 . In particular, as the container 100 moves in the seat 362 of the bottom rotary die 360 under the top die 366 , the top die 366 rolls over the side flanges 106 and 108 such that the lid material 334 and the first and second side seal flanges 106 and 108 of the container 100 are nipped between the die surfaces 366 a and 366 b of the top die 366 and the support surfaces 367 and 369 of the seat 362 of the bottom die 360 . Since the top die 366 applies sealing pressure against the flexible side seal flanges 106 and 108 of the container 100 , the support surfaces 367 and 369 of the seat 362 provide support to and prevent the bending and/or breaking of the side seal flanges 106 and 108 , respectively, similarly to the support arm 352 at the tacking station 330 .
After the seat 362 of the bottom die 360 passes under the top die 366 and the lid material 334 is sealed to the side flanges 106 and 108 of the container 100 , the seat 362 travels under the second top die 368 . The second top die 368 seals the lid material 334 to the leading and trailing seal flanges 102 and 104 of the container 100 . In particular, as the container 300 passes under the top die 368 , first the lid material 334 and the leading seal flange 102 are nipped between the die surface 368 a of the top die 368 and the support surface 363 of the seat 362 of the bottom die 360 .
Then, the lid material 334 and the trailing flange 104 of the container 100 are nipped between the die surface 368 a and the support surface 365 of the seat 362 of the bottom die 360 . Since the top die 368 applies sealing pressure against the side flanges 106 and 108 of the container 100 , the support surfaces 363 and 365 of the seat 362 provide support to and prevent the bending and/or breaking of the leading and trailing seal flanges 102 and 104 of the container 100 , respectively, similarly to the support arm 352 at the tacking station 330 .
Since the support surfaces 367 and 369 of the seat 362 as well as the side flanges 106 and 108 are non-planar, the first and second top sealing members 366 and 368 and their respective sealing surfaces 366 a , 366 b , and 368 a do not move only about the initial axes of rotation of the top sealing members 366 and 368 . In particular, as the die surfaces 366 a , 366 b , and 368 a of the top sealing members 366 and 368 travel along the respective sealing flanges 102 , 104 , 106 , and 108 , the top sealing members 365 and 368 can travel both in an upward direction relative to their initial axes of rotation and in a downward direction relative to their initial axes of rotation. As such, each sealing member 366 and 368 has a variable axis of rotation which can reciprocate, and the relative position of the container 100 and the top sealing members 366 and 368 can vary as the lid material 334 is being sealed to the container 100 .
The rotational speed of the bottom rotary die 360 and the top sealing members 366 and 368 may be constant during the sealing of the lid material 334 to the container 100 . Alternatively, the rotational speed of either one or both the top sealing members 366 and 368 may vary during the sealing of the lid material 334 to the container 100 .
The top sealing members 366 and 368 can apply a sealing pressure in a direction that is normal to the seal flanges 102 , 104 , 106 , and 108 of the container 100 . More specifically, the bottom surfaces of the top sealing members 366 and 368 can apply a sealing force that is perpendicular to a line tangential to the non-planar seal flanges 102 , 104 , 106 , and 108 of the container 100 . This can provide for a smoothing action that can eliminate undesired wrinkling of the lid material 334 as it is being applied to the container 100 . Any wrinkles upstream of the sealing point of contact can be eliminated by the top sealing members 366 and 368 as a seal is made at the next sealing point, especially since the sealing surfaces 366 a , 366 b , and 368 b of the top sealing members 366 and 368 travel continuously along the surfaces of the seal flanges 102 , 104 , 106 , and 108 from the leading end 110 to the trailing end 111 of the container 100 .
With reference to FIG. 15 , after the second top die 368 seals the lid material 334 to the trailing flange 104 of the container 100 , the container 100 is transferred back to the conveyor surface 312 . In particular, the leading end 316 of the conveyor surface 312 can have a loading platform 317 extending in a direction toward the bottom rotary die 360 . The loading platform 317 may have an upper surface 318 that is in the same horizontal plane as the conveyor surface 312 . Alternatively, the upper surface 318 of the loading platform 317 may be above or below the conveyor surface 312 , or may be angled relative to the conveyor surface 312 . The loading platform 317 can have a leading edge 319 .
As the seat 362 with a fully sealed container 100 is rotated by the bottom die 360 toward the loading platform 317 , the leading edge 319 of the loading platform 317 can lift the leading seal flange 102 from the support surface 363 of the seat 362 of the bottom die 360 . With the leading flange 102 being lifted, the forward motion of the bottom die 360 , can urge the trailing flange 104 and the side flanges 106 and 108 of the container 100 to be lifted off the remaining support surfaces 365 , 367 , and 369 , respectively, such that the container 100 can be ejected from the seat 360 and transferred onto the loading platform 317 . The loading platform 317 can be shorter than the container 100 and as such, when the sealed container 100 is transferred onto the loading platform 317 , a portion of the container 100 comes in contact with and is pushed onto the leading edge 316 of the downstream section of the conveyor surface 312 .
The conveyor surface 312 can be made from a material that has sufficient friction with the container 100 such that when a portion of the container 100 sits on or is in contact with the conveyor surface 312 , the container 100 can be pulled onto the conveyor surface 312 . If the flat portion of the conveyor surface 312 does not pull the container 100 off the loading platform 317 , one of the raised ribs 313 may facilitate the transfer of the container 100 from the loading platform 317 onto the conveyor surface 312 . Once back on the conveyor surface 312 , the containers 100 can travel along the conveyor surface 312 coward a packing or accumulating station such as known in the art.
With reference to FIGS. 17-22 , a second embodiment of a conveyor system 400 and method for applying a lid to the container 100 will now be described. Similarly to the first conveyor system 300 , the second conveyor system 400 can be used to seal the container 200 or any other container having one or more non-planar seal flanges.
The conveyor system 400 includes a tacking station 430 and a sealing station 470 . As the containers 100 pass through the tacking station 430 , lid material 434 is placed onto the containers 100 , and as the containers 100 pass through the sealing station 470 , the lid material 434 is sealed to the containers 100 to provide a cover and hermetic seal for the food product stored in the containers 100 .
The tacking station 430 is identical to the tacking station 430 described with reference to conveyor system 300 and will not be separately described here, but like reference numerals will be used to designate like parts. Instead of the tacking station 430 shown in FIG. 17 , the conveyor system 400 may include a tacking station with a pick and place device as described above in reference to the tacking station 330 .
As the containers 100 exit the tacking station 430 with the lid material. 434 tacked to the leading seal flange 102 , they travel in the machine direction toward the sealing station 470 . At the sealing station 470 , the section of the conveyor surface 412 has a gap and a bottom rotary die 460 rotates in the gap and protrudes above the conveyor surface 412 . The bottom rotary die 460 is identical to the bottom rotary die 360 described above in reference to the conveyor system 300 , and will not be described separately, but like numbers will be used to designate like parts.
Instead of two top rotating sealing members 366 and 368 , the conveyor system 400 includes a rotary top die or sealing member 466 positioned over the bottom rotary die 460 . The top sealing member 466 can have a plurality of dies or surface configurations 472 with matching profile geometry to the seats 462 of the bottom rotary die 460 , as shown in FIGS. 19-22 . The dies or surface configurations 472 of the top sealing member 466 can be continuously curved or non-planar to provide an involute shape. In particular, each die 472 has sealing surfaces 473 , 475 , 477 , and 479 sized and shaped to match the support surfaces 463 , 465 , 467 , and 469 , respectively, of the seats 462 of the bottom die 460 . While the bottom die 460 rotates in the machine direction, the top sealing member 466 rotates in a direction opposite to the bottom die 460 and opposite to the machine direction.
When a container 100 received in a seat 462 of the bottom rotary die 460 passes under the top sealing member 466 , the sealing surfaces 473 , 475 , 477 , and 479 and the support surfaces 463 , 465 , 467 , and 469 of the seat 462 of the bottom rotary die 460 come into contact with the lid material 434 and nip the lid material 434 and the seal flanges 102 , 104 , 106 , and 108 , respectively, of the container 100 to hermetically seal the lid material 434 to the container 100 . As shown in FIGS. 20 and 21 , a rubber or plastic insert 464 may surround the support surfaces 463 , 465 , 467 , and 469 of each seat 462 to compensate for variations in material and machine orientations.
In particular, as the container 100 seated in the seat 462 of the bottom die 460 passes under the top sealing member 466 , first the lid material 434 and the leading seal flange 102 of the container 100 are nipped between the sealing surface 473 of the top sealing member 466 and the support surface 463 of the seat 462 of the bottom die 460 as shown in FIG. 20 . As the top sealing member 466 and the bottom die 460 continue to rotate, the sealing surfaces 477 and 479 of the top sealing member 466 roll over the side seal flanges 106 and 108 and nip the lid material 434 to the support surfaces 467 and 469 of the seat 462 of the bottom die 460 .
Finally, the sealing surface 475 of the top sealing member 466 and the support surface 465 of the seat 462 of the bottom die 460 nip the lid material 434 and the trailing seal flange 104 to seal the lid material 434 to the container 100 such that the container 100 is hermetically sealed as shown in FIGS. 21 and 22 . Since the top sealing member 466 applies sealing pressure against the leading, trailing, and side seal flanges 102 , 104 , 106 , and 108 of the container 100 , the support surfaces 463 , 465 , 467 , and 469 of the seat 462 of the bottom rotary die 460 provide support to and prevent the bending and/or breaking of the seal flanges 102 , 104 , 106 , and 108 of the container 100 , respectively, similarly to the support arm 452 at the tacking station 430 .
The top sealing member 466 rotates about one axis of rotation and the bottom die 460 rotates about one axis of rotation which can be parallel to, or different from, the axis of rotation of the top sealing member 466 . As such, the sealing member 466 has a constant axis of rotation. Since the support surfaces 467 and 469 of the seat 462 of the bottom die 460 and the side flanges 106 and 108 of the container 100 are non-planar, the sealing surfaces 477 and 479 of the top sealing member 466 have a matching curvature and travel along the respective non-planar sealing flanges 106 and 108 without requiring the top sealing member 466 to travel out of its axis of rotation. It is to be appreciated that the top sealing member 466 and the bottom die 460 can have synchronized speeds of rotation. Further, it will be appreciated that the speed of rotation the sealing member 460 and the bottom die 466 can be synchronized with the speed of the conveyor surface 412 .
Thus, unlike the top sealing members 366 and 368 , which can reciprocate by traveling in and out of their axes of rotation, the top sealing member 466 can seal all seal flanges 102 , 104 , 106 , and 108 of the container 100 while traveling about only one constant axis of rotation. Similar to the sealing surfaces 366 a , 368 a , and 638 b of the top sealing members 366 and 368 , the sealing surfaces 473 , 475 , 477 , and 479 of the top sealing member 466 can provide a sealing force that is perpendicular to a line tangential to the non-planar seal flanges 102 , 104 , 106 , and 108 of the container 100 . This can provide for a smoothing action that can eliminate undesired wrinkling of the lid material 434 as it is being applied to the container 100 as discussed in more detail above in reference to the conveyor system 300 .
With reference to FIG. 17 , after the top sealing member 466 seals the lid material 434 to the trailing flange 104 of the container 100 , the hermetically sealed container 100 can be transferred from the seat 462 of the bottom rotary die 460 back to the conveyor surface 412 substantially as described above in reference to the conveyor system 300 . For example, the conveyor surface 412 may include a loading platform similar to the platform 317 described above in reference to the conveyor system 300 . Alternatively, the bottom die 460 may simply unload the sealed packages 100 onto the conveyor surface 412 due to its forward rotating motion. Once back on the conveyor surface 412 , the containers 100 can travel along she conveyor surface 412 toward a packing or accumulating station such as known in the art.
With reference to FIGS. 23-28 , a third embodiment of a conveyor system 500 and method for applying a lid to the container 100 will now be described. Similarly to the conveyor systems 300 and 400 , the conveyor system 500 can foe used to seal the container 200 or any other container having one or more non-planar seal flanges.
The conveyor system 500 includes a tacking station 530 and a sealing station 570 . As the containers 100 pass through the tacking station 530 , lid material 534 is placed onto the containers 100 , and as she containers 100 pass through the sealing station 570 , the lid material 534 is sealed so the containers 100 to provide a cover and hermetic seal for the food product stored in the containers 100 .
The tacking station 530 is identical to the tacking station 330 described with reference to conveyor system 300 and will not be separately described here, but like reference numerals will foe used to designate like parts. Instead of the tacking station 530 shown in FIG. 23 , the conveyor system 500 may include a tacking station with a pick and place device as described above in reference to the tacking station 330 .
The conveyor surface 512 includes a plurality of die seats 562 similar or identical in shape to the die seats 362 and 462 described in reference to conveyor systems 300 and 400 above. The die seats 562 form a so-called die train along the conveyor surface 512 . As the containers 100 exit the tacking station 530 with the lid material 534 tacked to their leading seal flanges 102 , the containers 100 travel along the conveyor surface 512 in the machine direction and are deposited into a respective die seat 562 on the conveyor surface 512 as shown in FIG. 23 .
The container 100 is positioned in the die seats 562 such that only the seal flanges 102 , 104 , 106 , and 108 of the container 100 protrude from the cavity formed in the die seat 562 . In particular, the seal flanges 102 , 104 , 106 and 108 of the container 100 rest on the support surfaces 563 , 565 , 567 , and 569 , respectively, of the die seat 562 . As shown in FIGS. 25 and 26 , a rubber or plastic insert 564 may surround the support surfaces 563 , 565 , 567 , and 569 of each die seat 562 to prevent to compensate for variations in material and machine orientations.
The conveyor system 500 includes a rotary top die or sealing member 566 positioned at the sealing station 570 over the conveyor surface 512 . The top sealing member 566 can be identical to the top rotary die or sealing member 466 described above in reference to the conveyor system 400 and where appropriate, like reference numerals will be used to describe like parts.
The rotary top sealing member 556 has a matching profile geometry to the seats 562 formed on the conveyor surface 512 , as shown in FIGS. 26-28 . In particular, the top sealing member 566 has a plurality of dies or surface configurations 572 with die sealing surfaces 573 , 575 , 577 , and 579 sized and shaped to match the support surfaces 563 , 565 , 567 , and 569 , respectively, of the die seats 562 . The dies or surface configurations 572 of the top sealing member 566 can be continuously curved or non-planar to provide an involute shape. The top sealing member 566 rotates in a direction opposite to the machine direction as shown in FIG. 23 . When a container 100 received in a die seat 562 passes under the top sealing member 566 , the sealing surfaces 573 , 575 , 577 , and 579 and the support surfaces 563 , 565 , 567 , and 569 of the seat 562 nip the lid material 534 and the flanges 102 , 104 , 106 , and 108 , respectively, of the container 100 to hermetically seal the lid material 534 to the container 100 .
In particular, as the container 100 seated in the seat 562 passes under the top sealing member 566 , first the lid material 534 and the leading flange 102 of the container 100 are nipped between the sealing surface 573 of the top sealing member 566 and the support surface 563 of the seat 562 as shown in FIG. 26 . As the seat 562 moves in the machine direction and the top sealing member 566 rotates, the sealing surfaces 577 and 579 of the top sealing member 566 roll over the side seal flanges 106 and 108 and nip the lid material 534 to the support surfaces 567 and 569 of the seat 562 , respectively.
Finally, the sealing surface 575 of the top sealing member 566 and the support surface 565 of the seat 562 nip the lid material 534 and the trailing seal flange 104 to seal the lid material 534 to the container 100 such that the container 100 is hermetically sealed as shown in FIGS. 27 and 28 . Since the top sealing member 566 applies sealing pressure against the leading, trailing, and side seal flanges 102 , 104 , 106 , and 108 of the container 100 , the support surfaces 563 , 565 , 567 , and 569 of the seat 562 provide support to and prevent the bending and/or breaking of the seal flanges 102 , 104 , 106 , and 108 of the container 100 , respectively, similarly to the support arm 552 at the tacking station 530 .
The top sealing member 566 rotates about one axis of rotation which can be parallel to conveyor surface 512 . Since the support surfaces 557 and 569 of the seats 562 and the side flanges 106 and 108 of the container 100 are non-planar, the sealing surfaces 577 and 579 of the top sealing member 566 have a matching non-planar shape and can travel along the respective non-planar sealing flanges 106 and 108 without requiring the top sealing member 566 to travel out of its axis of rotation. It is to be appreciated that the top sealing member 566 can have a synchronized speed of rotation relative to the speed of the conveyor surface 512 .
Thus, unlike the top sealing members 366 and 368 , which travel radially in and out of their initial axes of rotation, the top sealing member 566 can seal all seal flanges 102 , 104 , 106 , and 108 of the container 100 while traveling about only one axis of rotation. Similar to the sealing surfaces 366 a , 368 a , and 638 b of the top sealing members 366 and 368 , the sealing surfaces 573 , 575 , 577 , and 579 of the top sealing member 566 can provide a sealing force that is perpendicular to a line tangential to the non-planar seal flanges 102 , 104 , 106 , and 108 of the container 100 . This can provide for a smoothing action that can eliminate undesired wrinkling of the lid material 534 as it is being applied to the container 100 as discussed in more detail above in reference to the conveyor system 300 .
With reference to FIG. 17 , after the top sealing member 566 seals the lid material 534 to the trailing seal flange 104 of the container 100 , the hermetically sealed container 100 continues to move in the die seat 562 along the conveyor surface 512 until it reaches an accumulating or packing station.
Optionally, any of the methods described in conjunction with the conveyor systems 300 , 400 , and 500 can include the step of creating a pressure atmosphere in the package that urges the lid in a direction away from the food product stored in the package. Likewise, any of the methods described in conjunction with the conveyor systems 300 , 400 , and 500 can include the step of creating a protective atmosphere in the food package to increase a shell life of the food product stored in the package. Further it is to be appreciated that the sealing surfaces of the sealing members 366 , 368 , 466 , and 566 described in conjunction with the conveyor systems 300 , 400 , and 500 , respectively, can be made from metal or from a resilient material.
These teachings describe containers having non-planar seal flanges. The containers can be sealed using any one of the above-discussed methods geared toward sealing containers having non-planar seal flanges.
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 concept.
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A method of sealing a package containing a food product is provided. The method comprises applying a lid to a non-planar flange surrounding a periphery of the food package. The method comprises supporting at least a portion of the non-planar flange and progressively sealing the lid to the supported portion of the non-planar flange by applying pressure at one or more tangent points against the lid and the flange using a sealing member having a pressure applying surface that rotates about an axis of rotation and one of radially varies relative to the axis of rotation and the axis of rotation reciprocates.
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RELATED APPLICATIONS
[0001] This application is a Continuation of U.S. application Ser. No. 09/373,327, filed on Aug. 12, 1999, which claims the benefit of U.S. provisional application 60/096,268, filed on Aug. 12, 1998, the entire teachings of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] For many years, there has been large demand for live lobsters at areas distant from where the lobsters are harvested. To satisfy this demand, lobsters have been packaged and shipped great distances, including shipment by air transport.
[0003] In many instances, live lobsters were simply placed in large cartons, such as cardboard cartons lined with suitable insulation, for shipment. Ice, refrigerated gel packs or other cooling means were added to lower the temperature of the lobsters during shipment. Unfortunately, many of the lobsters were damaged or died during shipment in such containers due to injury resulting from their inevitable contact and smashing together caused by such handling and shipment.
[0004] An attempt to overcome such problems resulted in the shipping container described in U.S. Pat. No. 5,042,260. The container described in this patent is a carton large enough to accommodate a plurality of live lobsters with an intersecting array of partition walls introduced into the container to subdivide its interior into a plurality of compartments. Each compartment is configured to receive a single live lobster.
[0005] An improved container is disclosed in U.S. Pat. No. 5,218,923. The container described in this patent comprises a bottom section having a plurality of lobster holsters, each suitable for containing the body and tail of a single lobster in a manner which supports the claws of the lobster at the elbow. This container has an upper section with an interior void suitable for containing cooling means for the lobsters contained in the holsters within the bottom section of the container. The holsters provided by this container provide shock protection, hold the lobsters snugly in place in the event the box is tipped and provide supplemental thermal insulation to each individual lobster in addition to that provided by the outside walls of the container. Suspending the lobsters in the holsters of this container allows the lobsters to spread their claws providing access to the gill portions of the lobsters to facilitate the introduction of moisture and lower temperatures to the gills during shipment.
[0006] While the lobster container described in the aforementioned patents provide substantial advantages over the use of cardboard cartons and the like, they still have certain drawbacks. They are, for example, designed to contain only one specific crustacean, namely the clawed lobster, Homarus Americanus. They are not practical for shipping lobsters or other crustaceans having significant size variations nor for crustaceans having significant shape variations from Homarus Americanus, such as Spiny lobsters, crabs or shrimp.
[0007] In addition, these containers are generally limited to top-down cooling which provides uneven and uncontrollable temperature gradients between the top and bottom of the container. This can present serious problems since it is scientifically documented that temperature directly affects the health and mortality of crustaceans. Top-down cooling often results in hot spots, wide temperature swings and severe temperature gradients throughout the container. Additionally, there is no ability in these containers to regulate or provide higher temperatures for warmer water animals.
[0008] In general, these containers are designed for holding lobsters for short periods of time outside of their natural water environment. They are generally not designed for reuse and are certainly not designed to facilitate the storage of lobsters or other crustaceans in a wet holding facility. The use of such containers results in the lobsters being packed, unpacked and repacked several times between the point at which they are caught and the ultimate consumer. These containers do not have the ability to hold lobsters in sea water or a cooking vessel.
SUMMARY OF THE INVENTION
[0009] This invention relates to a blank for a multi-sided container for live crustaceans. This blank comprises a base member with one or more thermal conditioning wall members foldably connected to it. In addition, thermal infiltration barrier wall members opposite to the thermal conditioning wall member or members are also foldably connected to the base. The thermal conditioning wall member or members and infiltration wall member or members have partial side wall members extending substantially orthogonally from them in an aligned relationship whereby the thermal conditioning wall member or members and the infiltration barrier wall member or members can be folded to bring their partial side wall members into contact, thereby forming a multi-sided container for live crustaceans having one or more compartments.
[0010] The crustacean container of this invention is designed to hold and transport live crustaceans in or out of their natural environment. Crustaceans for this application include all types of lobsters, shrimp, prawns, crabs, fresh water crayfish or all animals in the biological classification of Crustacea. The container can be formed to fit each animal's anatomical shape and size. Temperatures can be adjusted by using different warming, cooling or freezing mediums and/or varying the thermal conductivity of the materials of construction. Conditioning circulation can be adjusted to control the air or water flow on one side or all sides of the animal. Shippers can reduce costs while improving product quality using this crustacean container. The custom shapes make it quick and easy to pack the animals. They can be packed by the fisherman on the boat, transferred through the various distributions and holding facilities, and boiled in the pot without reducing the quality of the animal by stressful handling during this long process. The shipper also has the flexibility of using any type or size outer packaging and the ability to reduce shipping and storage costs when the containers are empty by utilizing the nesting feature of the blanks for the container.
[0011] Biologically out of the water, the crustacean container provides the animals isolation, physical protection, humidity plus an even and controlled ambient temperature without stressful wide temperature swings and gradients. In the water, the crustacean container provides stress limiting isolation in a protected den, thus eliminating the need to fight for territories within the tank. The animals stay healthier. They can also be transferred from the fishing boat to the holding tanks of the various distributors, to the air cargo packers, to the distant last level distributor and to the consumer's cooking pot without the stresses caused by handling each individual lobster.
[0012] This crustacean container provides the shippers and their customers with a wide range of flexibility in holding and shipping options regardless of their geographical location. The nesting design of the open crustacean container gives the ability to pack a large quantity of crustacean containers in a relatively small amount of cubic volume. This gives shippers in remote seacoast areas of industrialized countries or newly industrialized countries access to the product at more reasonable freight costs. The ability to immerse the crustacean container in water allows the storage of animals in wet holding systems. Animals can be pre-graded and packed when labor is readily available and cheap. At shipping time, the animals can be drained and packed into an outer container without the stress of being directly touched again. Receivers of the animals can inspect the animals without removing them from the crustacean containers and can place the module directly into their tanks upon receipt, thus eliminating another stressful handling operation. The operation is again repeated when they are repacked by the receiver and shipped to another distributor or the ultimate customer. The structurally independent modular design of the crustacean container allows the flexibility of selecting any size or type outside shipping or storage container. The outer container can be selected to pack a large number or small number of animals per unit. Using different size crustacean container modules, one type of outer container can contain jumbo animals and small animals efficiently. The outer container can be non-insulated or insulated with varying thickness and insulating values. The modules are designed to conform to animals of different sizes, shapes and species. Different size modules can be mixed within an outer container to allow a wide range of sizes to be packed in the same box with each animal having a properly fitting cell. This unique design also eliminates the need for costly, volume consuming, labor intensive and unsanitary fillers and insulators such as organic straws, excelsior, cardboard, wood chips, newspapers, bubble packs, foam rubber, etc.
[0013] The crustacean container's unique design has a thermal conditioning wall with the ability to be configured to the shape of the animal and the animal's specific temperature requirements. The thermal conditioning wall can be perforated with various configurations to control the cooling flow to all or specific parts of the animal. The wall can also be insulated to reduce the temperature conduction for warmer water or tropical animals.
[0014] The crustacean container is designed to accommodate a variety of crustaceans. The flexibility in design accommodates various sizes, quantities and temperature requirements. It consists of a one piece formed unit that when laid flat is shaped to provide nesting of stacked units for compact storage and low cost shipping to packers. When ready to use, the design folds along predetermined hinges and is strongly held together with a series of strategically located locking devices. When locked together, the clamshell-like device forms a plurality of environmental chambers which will isolate, cushion, condition and restrain each animal. A crustacean container can be fabricated to hold any specified number of animals, and any number of crustacean container modules can be placed into any size or type shipping container. Thermal coolers could be used for long distance shipping or simple cardboard containers for shorter shipments where very high densities minimal insulation is required.
[0015] The crustacean container's two hollow side walls act to isolate the animal and as ventilating ducts which can be perforated according to the animal's temperature requirements. The thermal conditioning wall is uniquely angled and shaped to serve several functions. The bottom portion is shaped to accommodate the physical shape of the conditioning medium and the top section is shaped to follow the physiological shape of the animal. A larger thermal conditioning chamber can be constructed by placing two crustacean containers back to back. Shaping the wall to the specific animal minimizes the movement of the animal, thus consuming less oxygen. In addition, it can utilize the animal's appendages for support and shock absorption. Utilizing different elevations of the thermal conditioning wall optimizes the container volume to maximum density per cubic inch, giving lower transportation costs. The entire thermal conditioning wall serves as a header duct that can distribute the cool air to and through the side walls surrounding each animal, or it can restrict the air from entering the side walls for warmer animals. Unlike conventional containers, the thermal conditional wall design facilitates the maintenance of equal temperatures between the top and bottom of the container. Temperature control can also be affected by rotating the sensitive parts onto or away from the thermal conditioning wall. For example, the sensitive side of cold animals could be rotated toward the thermal conditioning wall or the sensitive parts of the warm water animals could be rotated away from the thermal conditioning wall. Further temperature control can also be accomplished by using different materials to form the crustacean container. The wall can be constructed with thermal conducting materials for direct transfer to the animals and thermal insulating materials for indirect transfer to the animals. The wall opposite the thermal conditioning wall is the infiltration barrier wall. It is placed along the outer shipping container's inside perimeter and shaped to fit the form of the animal. The air space formed between this wall and the inside wall of the shipping container also provides additional insulation and a means of directing the perimeter convection flow. The floor of the crustacean container can be perforated to serve two functions. These perforations function as waste drain holes during shipping and for water circulation while the containers are in holding systems. Unlike other partitioned containers, the unpacking time is very fast. There is no struggling to remove soggy materials, expanded polystyrene (EPS) beads or other messy debris. The hinged clam shell is simply opened, as a book, and all of the animals are easily accessible for removal.
[0016] The crustacean container can be loaded with animals well in advance of actual shipping time, placed in the wet holding system, and then placed in the outer shipping container at the last possible moment. This will allow the labor intensive grading and packing to take place when the labor resources are available. The modular aspect of the crustacean container allows the packer to define the number of crustacean containers packed into each shipping container. When the consignee receives the animals, the crustacean container modules can be placed into the wet system without handling and stressing each lobster. When the consignee ships an order, the consignee can remove only the required quantity of crustacean containers, without additional handling labor and stress to the animals.
[0017] The crustacean container can be constructed of many moldable materials. It can be totally impervious to moisture. It can also be constructed so as not to generate contaminants or particles while it is being handled. Some material choices may be transparent for visual non-contact quality assessment, or opaque materials may be used for marketing appeal. Food grade or non-food grade materials can be employed. Using high temperature materials, the animals can be cooked within the module, thus reducing the risk of injury and the discomfort associated with touching a live animal. Thickness of the material can be varied for different requirements. Thick materials may be used for greater structural integrity which may be required for greater shipping protection or for reusable modules. The use of thinner materials may be an option for smaller animals, to lower costs or for disposable units, when protection is not as critical.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.
[0019] [0019]FIG. 1 is a perspective view of a partially closed blank for a crustacean container according to this invention which, when folded into place, provides a crustacean container having six crustacean compartments.
[0020] [0020]FIG. 2 is an end view of two crustacean containers of FIG. 1 positioned back-to back, with one fully closed and one partially closed illustrating, inter alia, the positioning of conditioning medium in a thermal conditioning chamber formed between the backs of the two containers.
[0021] [0021]FIG. 3 is a cut-away side view illustrating the positioning of a Spiny lobster in one compartment of a crustacean container according to this invention.
[0022] [0022]FIG. 4 is a cut-away side view illustrating one option for packing a clawed lobster in a compartment of a crustacean container according to this invention.
[0023] [0023]FIG. 5 is a perspective view of an alternative embodiment of a crustacean container formed from a blank according to this invention and suitable for packing clawed lobsters in a second option.
[0024] [0024]FIG. 6 is a cut-away end view illustrating a clawed lobster packed in a compartment of the container of FIG. 5.
[0025] [0025]FIG. 7 is a perspective view of another embodiment of a crustacean container according to this invention suitable for containing crabs.
[0026] [0026]FIG. 8 is a cut-away end view of the container of FIG. 7 illustrating the packing of a crab in one of the compartments.
[0027] [0027]FIG. 9 is another embodiment of a crustacean container according to this invention suitable for containing shrimp or crayfish in its multiple compartments.
[0028] [0028]FIG. 10 is a cut-away end view of a crustacean container according to this invention illustrating the packing of shrimp into the compartments of the container.
[0029] [0029]FIG. 11 is another embodiment of a crustacean container according to this invention employing a corrugated form with containment flaps and no ducted side walls.
[0030] [0030]FIG. 12 is a perspective view of a crustacean container according to this invention packed into a standard cardboard container.
[0031] [0031]FIG. 13 is a perspective view of a crustacean container according to this invention loaded into an insulated outer cardboard container.
[0032] [0032]FIG. 13A is a perspective view of a crustacean container according to this invention loaded first into a plastic bag and subsequently into an insulated cardboard container.
[0033] [0033]FIG. 14 is a perspective view of a crustacean container according to this invention loaded into a wire cage useful for wet storage of crustaceans.
[0034] [0034]FIG. 15 illustrates a crustacean container according to this invention loaded into a standard fish tote suitable for wet storage of crustaceans contained in the container.
DETAILED DESCRIPTION OF THE INVENTION
[0035] The above features and other details of the crustacean container of this invention will now be more particularly described with reference to the accompanying drawings and pointed out in the claims. The same number present in different figures represents the same item. It will be understood that the particular embodiments for the invention are shown by way of illustration and not as limitations of the invention. The principal features of the invention can be employed in various embodiments without departing from the scope of the invention.
[0036] A partially closed blank 8 for a crustacean container suitable for six crustaceans is depicted in FIG. 1. Blank 8 contains side walls 10 and 10 ′, thermal conditioning wall 11 , infiltration barrier wall 12 and module floor 13 . The unassembled blank 8 lays flat in its unfolded position and its geometry is designed to allow voids 14 of the side walls 10 and 10 ′ to nest into each other for high density economical storage and transportation. Assembly is accomplished simply by folding blank 8 at two folding hinges 15 joined to the blank floor 13 . The blank floor 13 can be perforated to allow drainage of animal waste out of the module or for enhanced water circulation while the container is in a water holding system.
[0037] Blank 8 can be constructed using a wide variety of forming processes. It can, for example, be thermo-formed, vacuum formed or produced by other molding and/or forming techniques. This allows great flexibility in forming compound shapes, which is not usually possible with EPS, sheet plastics or cardboard. This also provides for the ability to use a wide range of water and moisture resistant materials and laminates to address each crustacean's and each shipper's specific requirements. For example, the material can be thermally conductive, insulating or a laminated combination. It can be economically molded or die cut to provide custom ventilating configurations. It can also be thick for applications with larger animals requiring superior structural integrity or durability for constant reuse. On the other hand, it can be thin for lightweight disposable applications or smaller animals. The material can be transparent for animal visibility or can be an opaque coloring for various marketing reasons. It can also be made to withstand the low temperature of dry ice or other cooling means or the high temperature of boiling water.
[0038] The folded container is held together by locking devices formed by tabs 17 located on an edge of the side walls 10 and intended to be inserted into companion receiving holes 17 ′ on the opposite edges of side walls 10 ′. Locking base 18 also helps lock the side walls 10 and 10 ′ into the closed container position. When the cells are locked into place, they form rigid self-supporting compartmentalized modules. The shape and curvature of side walls 10 and 10 ′ can be shaped to conform to specific animal anatomies. In addition to providing isolation, side walls 10 and 10 ′ can provide the vital function of temperature control. Using thermally conductive material, they can act as cooling or heating plates. Also, each wall can be punched or trimmed to provide a variety of ventilating schemes for heating or cooling. For example, holes 20 can be punched in various locations along the side walls 10 or the side walls 10 can include vents 21 positioned along the leading edge of side walls 10 , or both.
[0039] The dimensions of the crustacean container will vary depending upon its ultimate use. As an example, if the six compartment container illustrated in FIG. 1 is designed for clawed lobsters, it might have an overall length of about 21½ inches, a width of about 4 inches and a height about 8½ inches.
[0040] [0040]FIG. 2 illustrates how two containers of FIG. 1 might be placed in a back-to-back relationship providing a thermal conditioning chamber 22 in which temperature conditioning medium, such as a gel pack 23 , might be placed.
[0041] Thermal conditioning wall 11 serves several functions. The entire surface of wall 11 , when containers are placed in a back-to-back relationship as in FIG. 2, provides a chamber 22 in which thermal conditioning medium, such as gel pack 23 , can be placed. The upper portion of wall 11 can be shaped to conform to the particular crustacean to be packed. For example, the upper portion of wall 11 can be shaped and angled to form a support and nest for the specific animal. The multiple functions of the surface of wall 11 , at different elevations, ensure the maximum utilization of the critical internal space of each compartment. The entire wall, its upper and lower portions, can be used as a thermal conditioning surface, a main thermal distribution duct or a combination of both. Materials of construction can be selected to best fit the thermal requirements for the specific crustacean to be packed. This will ensure the control of temperature throughout the entire module at all elevations within the compartment.
[0042] Infiltration barrier wall 12 is positioned opposite the thermal conditioning wall 11 . The infiltration barrier wall 12 can also be shaped to fit the specific animal. It also directs the convection or the air infiltrating the outer container and forms one of the five walls defining the cell. Side walls 10 can also act as infiltration barriers.
[0043] Unloading the container is achieved by simply unlocking the side wall locks by pulling the thermal conditioning wall 11 and infiltration barrier wall 12 apart, thereby exposing the crustaceans. Crustaceans can be easily and quickly removed piece by piece or simply dumped. Because the animals are totally exposed, there is no additional stress placed on the animals by having to pull or force their appendages that may be embedded in the fixed side of containers of the prior art.
[0044] A typical use for the crustacean container of the present invention, namely in containing Spiny lobsters, is illustrated in FIG. 3. The treatment of the antennae on Spiny lobsters is critical to the lobsters' health. They are sensory, offensive and defensive weapons. The objective is to restrict and anesthetize them while maximizing the container volume. As shown in FIG. 3, the Spiny lobster is placed into the crustacean container with its tail 30 at the bottom of the compartment and its temperature sensitive underside 31 facing away from thermal conditioning wall 11 . The antennae 32 are bent backward along the back side of the Spiny lobster to achieve several functions. First, the rigid antennae hold the warmer water animal away from direct contact with the cooler thermal conditioning wall 11 . Second, the extra-sensitive sensory receptors along the antennae are anesthetized by being in direct contact with the thermal conditioning wall 11 . Cooling of the antennae reduces the activity of the animal and thus reduces stress during shipment. Third, the tensions the antennae placed against the thermal conditioning wall 11 wedge the lobster into its compartment, thus reducing movement during handling. The method of folding the antennae back also facilitates easier and faster packing. Once placed into the compartment, the lobster is immobilized, unlike conventional packing where one must hold the animal in place with one hand while trying to pack filler materials around the moving animal to keep it immobile. When the container, with the animal inside, is placed in a holding tank, the restricted antennae cannot be used by the animal in an aggressive manner, thus reducing stress and improving quality.
[0045] For clawed lobsters or Homarus Americanus, two embodiments of suitable crustacean containers according to this invention are illustrated in FIGS. 4, 5 and 6 . Both employ vertical orientation of the lobster loaded with its tail 40 placed at the bottom of the compartment. In FIG. 4, the first option illustrates the packing of a clawed lobster in a compartment with its underside positioned close to the thermal conditioning wall 11 . This is ideal for a clawed lobster, a cold water animal, because it results in the sensitive underside of the clawed lobster being in direct contact with the thermal conditioning wall 11 .
[0046] The second method for employing a crustacean container of the present invention for clawed lobsters is illustrated in FIGS. 5 and 6. In this embodiment, the container has a 90 degree step in its thermal conditioning wall. A cooling chamber 43 is formed by the vertical portions 44 and the horizontal portion 45 of the thermal conditioning wall. It has a lower profile to maximize space when the animal is rotated 90 degrees. The left claw of the lobster receives additional support from the horizontal portion 45 of the thermal conditioning wall. The wider top causes the claws 46 to be drawn in closer to the animal, as illustrated in FIG. 6, thus reducing the height and maximizing the internal volume. The sensitive underside of the lobster is positioned against side walls 47 of the compartment. To maximize cooling in this area, cold air could be ducted from the chamber 43 and directed through the side walls. This method is an efficient utilization of the interior volume of the container.
[0047] A crustacean container according to this invention suitable for containing crabs is illustrated in FIGS. 7 and 8. As illustrated in FIG. 7, this container is shaped to fit crabs and consists of an upper section 70 and a lower section 71 which stack on top of each other. Lower section 71 employs a thermal conditioning wall 74 which is high enough to nest into and support the shorter thermal conditioning wall 75 of the upper portion 70 . Upper portion 70 straddles the top of the lower portion 70 . This configuration includes a conditioning wall 74 which is common to both upper portion 70 and lower portion 71 , thus utilizing one common conditioning medium for both levels to maximize the internal volume. Packing of a crab 76 in one of the compartments of the container illustrated in FIG. 7 is illustrated in FIG. 8. The compartments are shaped to conform to smaller animals. They are loaded in the same manner as the lobster, namely with the tail down and the underside positioned against the thermal conditioning wall. The orientation could change 180 degrees if warm water shrimp were employed.
[0048] Another embodiment of a crustacean container according to this invention which is suitable for the packing of shrimp and crayfish is illustrated in FIGS. 10 and 11. The internal volume is maximized by employing a corrugated shape to form cells 90 . The corrugated design furnishes three sides, 91 , 92 and 93 . The fourth side of the compartment is furnished alternately by thermal conditioning wall 94 on one side and the folding flaps 95 and 96 , on the opposite sides. This eliminates the hollow side walls to conserve space. Cooling is achieved directly from the thermal conditioning wall 94 .
[0049] It is possible, of course, to use the crustacean containers according to this invention with other types of outer containers. Some of these will now be illustrated.
[0050] In FIG. 12, two six-container crustacean containers are illustrated in a back-to-back relationship packed into a standard cardboard box.
[0051] Similarly, FIG. 13 illustrates how these containers might be placed in a cardboard container with thermally insulating material 28 .
[0052] [0052]FIG. 13A illustrates a similar arrangement but with the addition of a gas-tight polymer bag 98 surrounding the back-to-back crustacean containers. It should be noted that the container compartments act as a shield between the spines on Spiny lobster, for example, and the polymer bag, thereby ensuring that the spines do not puncture the bag and release gasses contained therein. Gasses, such as oxygen, contained within the polymer bag help to provide a less stressful environment for the animals.
[0053] [0053]FIG. 14 depicts two six-compartment crustacean containers placed in a back-to-back relationship and inserted into a cage or wire-type container 99 for wet storage. Such an arrangement could be used, for example, by fishermen on boats or distributors at live lobster holding facilities.
[0054] [0054]FIG. 15 illustrates four seven-compartment crustacean containers placed in a back-to-back relationship and then inserted into a conventional fish tote 100 . The draft angles of the container walls and the draft angle of the fish tote will form a wedge. When a group of containers are inserted into the tote, as shown, they wedge tightly into it. The wedge prevents the crustacean container from reaching the bottom of the tote, leaving a space for water circulation and waste isolation between the bottom of the tote and the bottom of the crustacean container. As shown, the bottom of each tote has a number of drain holes. When the totes are stacked on top of each other, with a water supply over the top tote, the water cascades from the top tote to the bottom tote through the holes in the bottoms.
[0055] A large hole at the bottom of the end wall of each tote is employed to facilitate the flushing of waste and other biological matter that has settled in the space between the bottom of the container and the tote. This flushing technique is especially useful when using the system for long term holding, where residual unconsumed food needs to be evacuated. Flushing can be enhanced by injecting pressurized water from the end opposite the flushing outlet or by gravity. The gravity flushing method can be achieved by tilting the stack of totes on the side opposite the flushing outlet, allowing the water and waste in the tote to drain out the lower end.
[0056] The container described herein was designed for crustaceans. However, it can also be employed to store or contain other marine animals, or for that matter, other goods, particularly fragile goods.
EQUIVALENTS
[0057] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the inventions described herein. These and all other equivalents are intended to be encompassed by the following claims.
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A blank for forming a multi-sided container suitable for storing and/or shipping live crustaceans, such as lobsters, shrimp, and crayfish is disclosed. The blank has a base member to which one or more thermal conditioning wall members are foldably connected. In addition, one or more infiltration barrier wall members are foldably connected to the base opposite the thermal conditioning wall member or members. The thermal conditioning wall member or members and infiltration wall member or members have partial side wall members extending substantially orthogonally from them in an aligned relationship. Thus, the thermal conditioning wall member and infiltration barrier wall member can be folded to bring their partial side wall members into contact, thereby forming one or more multi-sided containers for live crustaceans.
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CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional App. No. 61/940,840, Attorney Docket No. DMAR-001-1P, filed on Feb. 18, 2014, which is incorporated herein by reference.
FIELD OF PRESENT DISCLOSURE
[0002] This present disclosure relates to bending testing.
BACKGROUND INFORMATION
[0003] During oil and gas underwater field development, some more and more commonly used subsea equipment include slender structures such as umbilicals, flexibles, and rigid pipes. These slender structures have strong non-linear bending characteristics. Thus, linearized approximations of the bending stiffness of these slender structures are oftentimes not sufficient for ascertaining the bending characteristics of such structures. At the same time, the more complex non-linear bending characteristics cannot be derived directly from theoretical calculations alone. Apparatus and methods have been proposed for conducting bending testing to obtain the accurate bending characteristics of these slender structures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] In the drawings:
[0005] FIG. 1 is a diagram showing the overview of an embodiment of the bending testing apparatus;
[0006] FIG. 2 is a diagram showing the top view of an embodiment of the bending testing apparatus; and
[0007] FIG. 3 is a diagram showing the zoomed-in view of the pattern of the holes pre-drilled on the testing platform of an embodiment of the bending testing apparatus.
DETAILED DESCRIPTION
[0008] This document discloses apparatus and methods related to bending testing. FIG. 1 shows an implementation of the apparatus and methods for bending testing. The bending testing for a testing sample 11 can be performed on a testing platform 12 . The testing sample 11 is fastened by two fasteners 13 A and 13 B on each end. The fasteners 13 A and 13 B are further attached to two extendable and retractable arms 14 A and 14 B that can be attached to the testing platform 12 . The fasteners 13 A and 13 B can be clamps, which can be further attached to the extendable and retractable arms 14 A and 14 B through two pivot pins 15 A and 15 B (or chain links, shackles, or other devices). The extendable and retractable arms 14 A and 14 B can be two hydraulic cylinders, winches, or other tensioning devices. The testing sample 11 can be positioned on the testing platform 12 along one or more pellets 17 A, 17 B, and 17 C. The pellets 17 A, 17 B and 17 C can be attached to the testing platform 12 by fitting into the pre-drilled holes 16 on the testing platform 12 . The pre-drilled holes 16 can be arranged in a defined pattern. For example, the pattern can be defined according to the formula X=R*sin[L/R], and Y=R*(cos[L/R]−1), wherein R is the bending radius, L is the sample half length, and X and Y are the coordinates for the pre-drilled holes 16 on the testing platform 12 . The pellets 17 A, 17 B and 17 C can be placed into the pre-drilled holes according to a defined pattern to help maintain a certain shape or curvature of the testing sample 11 .
[0009] FIG. 2 shows the top view of an implementation of the apparatus and methods for bending testing. A plurality of pellets is used to help maintain a uniform curvature and constant bending radius.
[0010] FIG. 3 shows the zoomed-in view of the pattern of the holes pre-drilled on the testing platform of an implementation of the apparatus and methods for bending testing. The pellets can tightly fit in the pre-drilled holes on the testing platform, and can be moved from one hole to another based on the desired shape and curvature. The pellets can have threads at one end. The pellets can also be attached to the testing platform through a separate nut. The pellets can also have lock pin holes, and can be attached to the testing platform through a locking pin.
[0011] In some implementations, the testing sample can be about five meters in length. Two clamps can be used to hold the two ends of the testing sample, and prevent slippage between adjacent parts of the testing sample, such as umbilical tubes or flexible layers. The clamps can have pivot pins to allow them to rotate freely, and the pivot pins can be controlled by a tensioning device, such as hydraulic cylinders. The hydraulic cylinders can pull the testing sample to wrap around the pellets, and the hydraulic cylinder pulling loads can be recorded.
[0012] In some implementations, the bending testing can be conducted as follows: (i) lay the testing sample on the testing platform; (ii) fasten the ends of the testing sample; (iii) position the pellets to the arc with desired radius; (iv) activate the hydraulic cylinders to pull the testing sample against the pellets; and (v) record the hydraulic cylinder tension time histories. From the tension time histories, the minimum tension required to achieve the desired bending radius can be derived. This minimum tension can then be decomposed into testing sample axial direction and normal direction, based on which the bending moment can be calculated. This bending moment can be the output of the testing result. When the steps above are completed, the hydraulic cylinders can be slacked slightly, and the pellets can be moved to the next testing radius, so that additional tests can be repeated at different radiuses.
OTHER EMBODIMENTS
[0013] Various other adaptations and combinations of features of the embodiments and implementations disclosed are within the scope of the present disclosure. 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. Other aspects, advantages, and modifications are within the scope of the following claims.
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Apparatus and methods related to bending testing are described. For example, some embodiments may contain a clamp with pivot pin, pellet, tensioning device, and supporting platform, which can be used for testing the bending characteristics, such as bending stiffness, of a testing sample, which can be slender structures such as umbilicals, flexibles, and rigid pipes.
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BACKGROUND OF THE INVENTION
The present invention relates to an Internet information displaying apparatus for receiving information through the Internet, converting the information into video signals, and displaying the information on a CRT display or the like.
Recently, due to the wide popularity of personal computers, information is transmitted and received widely by using the Internet.
The Internet is a network of multiple computers connected on a global scale, and various pieces of readable information are stored in individual computers. These pieces of information include E-mails, various programs, and home pages, which can be communicated in two ways. The home page corresponds to the title and table of contents of a piece of information, and by selecting a graphic pattern (icon) or a word on the home page, the necessary information can be accessed and reviewed.
Therefore, recently, more and more users are using the Internet as the preferred mode of information presentation. It is the WWW (World Wide Web) that is typically used as the server for providing such information.
The reason why the WWW server is drawing attention is mainly due to the wide spread of the client software (browser) for retrieving information by using a graphical menu. By the development of such a browser, it became easier to search information on the Web, and the traffic volume to the WWW server increased significantly. Users of the WWW have come to notice the web as a publicity and advertising media, and many users are utilizing the web at any given time.
To read information on the WWW server, as mentioned above, a browser is needed. For example, a browser is disclosed in pages 164 to 167 of “Internet Handbook for Corporate Users”, an extra output of Nikkei Communications published by Nikkei BP (Nov. 30, 1994). In order to view the information on the WWW server by the Internet, conventionally, it is necessary to install the browser in the personal computer.
FIG. 1 is a schematic diagram showing a conventional connection example of computer and Internet. In this connection example, a personal computer 107 is connected to a communication line 102 through a modem 108 or a terminal adapter, and through the communication line 102 , it is further connected to a modem 103 or a terminal adapter of a provider which is a connection service firm. The modem 103 is connected to a server 104 which is the computer of the provider.
The server 104 is connected to the Internet 106 around the clock through a router 105 for setting a trunk route.
From the personal computer 107 , a telephone call is made when necessary, and a connection is made to the Internet 106 through the server 104 of the provider (dial-up connection).
Among those not owning personal computer, there are many people wanting to use the Internet, but not willing or able to buy a personal computer. Some are hesitant to operate a personal computer. Among those people, it seems many people want to use the Internet, if possible, without using a personal computer.
In view of this hesitation on the part of many individuals, Internet television allowing use of the Internet easily by the television receiver is proposed. That is, the Internet information is displayed by using the television receiver in the general household as the display of the personal computer. Accordingly, without having to purchase a personal computer, only a device for receiving the Internet information is built in or attached to the television receiver, and such device is easy to handle as compared with the personal computer, and the television receiver performs its original function while not reviewing the Internet information, which is very convenient for the user.
However, to review the information of WWW server of the Internet by such television receiver, it is necessary to connect once to the provider through the communication line. Only by connecting the communication line with the provider, the information can be acquired.
The connection by the communication line is made through a modem, and the users of personal computer who make communications can determines if an appropriate connection is made or not as follows. That is, since the modem is sending data by sound signal and can be monitored, it is determined if the data is communicated or the telephone is connected by the sound.
Incidentally, when a function for receiving the Internet is incorporated in the television receiver, it is possible to watch the television broadcast while the modem is connecting to the provider, and such function is generally desired because the user can be entertained by the broadcast while waiting for the connection connected.
However, in case of receiving a television broadcast by television receiver or the like, it is usual for the sound of the television broadcast to be cast on a speaker of a receiver. In such case, in connecting a communication line, the determination of whether or not the connection is made by the sound from the modem cannot be made because the sound from the modem cannot be heard due to the casting through the speaker of the sound from the television broadcast.
The above fact is the same not only in the case of viewing the television program on the television broadcast but also while viewing the video signals from the VTR (video tape recorder) or LD (laser disk) player.
The present invention has been developed in the light of the situation as above, and its principal object is to make the condition of the telephone line connection easily recognizable even under the condition where the video signal such as a television signal is being received and the sound from the video signal is outputted from the speaker in an Internet information displaying apparatus like a television receiver having Internet receiving capabilities.
SUMMARY OF THE INVENTION
An Internet information displaying apparatus according to the present invention includes, in a first embodiment, television signal receiving means for receiving a television signal, and video signal outputting means for outputting a video signal by extracting from the television signal received by the television signal receiving means. Displaying means are provided for displaying the video signal outputted by the video signal outputting means, and sound signal outputting means are provided for outputting a sound signal extracted from the television signal received by the television signal receiving means; audible sound generating means for generating the sound signal as audible sound outputted by the sound signal outputting means. Modulating/demodulating means transmit and receive the digital data through a telephone line by converting the digital data into a carrier signal by sound for transmission, and by demodulating the carrier signal into digital data when receiving. Data converting means are provided for transmitting the digital data to the modulating/demodulating means and for receiving the digital data from the modulating/demodulating means, and for converting the received digital data into a video signal. Converted video signal outputting means are provided for outputting the output from the data converting means to the displaying means. Carrier signal outputting means are provided for outputting the carrier signal by the transmitting/receiving sound of the modulating/demodulating means. Telephone line sound outputting means provide sound signal generated in the telephone line to the audible sound generating means and generating as audible sound.
A second embodiment of the Internet information displaying apparatus according to the present invention also includes character signal generating means for generating a character signal and outputting it to the displaying means and character signal generation controlling means for detecting a transmitting/receiving condition of the digital data by the modulating/demodulating means, and controlling the character signal generating means so as to generate a character signal to indicate the transmitting/receiving condition.
A third embodiment of the Internet information displaying apparatus according to the present invention is such that, in the first and the second embodiments, the telephone line sound outputting means inputs the signal including the carrier signal from the carrier signal outputting means, and outputs it by mixing with the sound signal to the audible sound generating means.
A fourth embodiment of the Internet information displaying apparatus according to the present invention is that the first embodiment further includes sound volume controlling means for controlling the sound signal outputting means.
A fifth embodiment of the Internet information displaying apparatus according to the present invention is such that, in the fourth embodiment, the sound volume controlling means controls the output level of the sound signal from the sound signal outputting means to become lower in case of mixing the output from the telephone line sound outputting means and outputting it to the audible sound generating means.
A sixth embodiment of the Internet information displaying apparatus according to the present invention is such that, in the fourth embodiment, the sound volume controlling means controls the output level of the sound signal from the sound signal outputting means to be “0” in case of mixing the output from the telephone line sound outputting means and outputting it to the audible sound generating means.
A seventh embodiment of the Internet information displaying apparatus according to the present invention includes television signal receiving means for receiving a television signal, and video signal outputting means for outputting a video signal by extracting from the television signal received by the television signal receiving means. Displaying means are provided for displaying the video signal outputted by the video signal outputting means, and sound signal outputting means are provided for outputting a sound signal by extracting from the television signal received by the television signal receiving means. Audible sound generating means are provided for generating the sound signal as audible sound outputted by the sound signal outputting means, end dial sound generating means are provided for generating a signal of the dial sound from a telephone line. Modulating/demodulating means are provided for transmitting and receiving the digital data through a telephone line by converting the digital data into a carrier signal by sound at transmitting, and by demodulating the carrier signal by sound into digital data at receiving. Data converting means are provided for transmitting digital data to the modulating/demodulating means and receiving digital data from the modulating/demodulating means, and converting the received digital data into a video signal. Converted video signal outputting means are provided for outputting the output from the data converting means to the displaying means, and carrier signal outputting means are provided for outputting the carrier signal by the transmitting/receiving sound of the modulating means. Telephone line sound outputting means for outputting the dial sound signal and the carrier signal to the audible sound generating means.
An eighth embodiment of the Internet information displaying apparatus according to the present invention is that the seventh embodiment further includes character signal generating means for generating a character signal, and outputting it to the displaying means. Character signal generation controlling means detect a transmitting/receiving condition of the digital data by the modulating/demodulating means, and control the character signal generating means so as to generate a character signal to indicate the transmitting/receiving condition.
Further, a ninth embodiment of the Internet information displaying apparatus according to the present invention is such that, in the seventh and eighth embodiments, the telephone line sound outputting means controls to make the signal level of the dial sound to be outputted lower according to the dial sound signal generated by the dial sound generating means.
Further, a tenth embodiment of the Internet information displaying apparatus according to the present invention is such that, in the seventh and eighth embodiments, the telephone line sound outputting means controls to make the signal level of the dial sound to be outputted lower in case the dial sound outputted from the dial sound generating means is a pulse type.
A eleventh embodiment of the Internet information displaying apparatus according to the present invention is such that, in the seventh and eighth embodiments, the telephone line sound outputting means inputs the signal including the carrier signal from the carrier signal outputting means, and outputs it by mixing with the sound signal to the audible sound generating means.
Further, a twelfth embodiment of the Internet information displaying apparatus according to the present invention is such that the seventh and eighth embodiments further comprise pseudo dial sound generating means for outputting a signal of pseudo dial sound instead of the dial sound from the telephone line sound outputting means.
A thirteenth embodiment of the Internet information displaying apparatus according to the present invention is such that, in the twelfth embodiment, the telephone line sound outputting means outputs the signal of pseudo dial sound generated by the pseudo dial sound generating means according to the dial sound signal generated by the dial sound generating means.
A fourteenth embodiment of the Internet information displaying apparatus according to the present invention is such that, in the twelfth embodiment, the telephone line sound outputting means outputs the signal of pseudo dial sound generated by the pseudo dial sound generating means instead of the dial sound signal from the telephone line sound outputting means, in case the dial sound from the dial sound generating means is a pulse type.
Further, a fifteenth embodiment of the Internet information displaying apparatus according to the present invention is such that, in the twelfth embodiment, the telephone line sound outputting means inputs the signal including a carrier signal from the carrier signal outputting means, and outputs it by mixing with the sound signal to the audible sound generating means.
The above and further objects and features of the invention will more fully be apparent from the following detailed description with accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram showing the conventional example of connection of a computer with Internet;
FIG. 2 is a schematic diagram showing an example of connection of an Internet television as an Internet information displaying apparatus according to the present invention with Internet;
FIG. 3 is a block diagram showing an example of constitution of the first embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 4A is a flow chart showing an example of operation of the first embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 4B is a flow chart showing an example of operation of the first embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 5A is a schematic diagram showing an example of screen display of the first embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 5B is a schematic diagram showing an example of screen display of the first embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 5C is a schematic diagram showing an example of screen display of the first embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 6 is a flow chart showing an example of operation of the second embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 7 is a time chart showing an example of operation of the second embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 8 is a block diagram showing the constitution of the third embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 9 is a flow chart showing an example of operation of the third embodiment of the Internet information displaying apparatus according to the present invention;
FIG. 10A is a schematic diagram showing an example of screen display of conventional Internet information displaying apparatus;
FIG. 10B is a schematic diagram showing an example of screen display of conventional Internet information displaying apparatus;
FIG. 10C is a schematic diagram showing an example of screen display of conventional Internet information displaying apparatus;
FIG. 11 is a block diagram showing an example of constitution of the fourth embodiment of the Internet information displaying apparatus according to the present invention; and
FIG. 12 is a time chart showing an example of operation of the fourth embodiment of the Internet information displaying apparatus according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, embodiments of the present invention will be illustrated with reference to the drawings.
FIG. 2 is a schematic diagram showing an example of connection of an Internet television as an Internet information displaying apparatus according to the present invention.
According to this connection example, the Internet television 101 , having a built-in modem, is connected with a communication line 102 . The communication line 102 is connected with a modem 103 or a terminal adapter of a provider which is a connection service company, and the modem 103 is connected to a server 104 which is a computer of the provider.
The server 104 is connected to the Internet 106 around the clock, through a router 105 for setting the trunk route.
By predetermined operation, a telephone call operation is automatically made from the Internet television 101 , and connection is made with the Internet 106 through the server 104 of the provider (dial up connection).
FIG. 3 is a block diagram showing an example of constitution of the first embodiment of the Internet television receiver as an Internet information displaying apparatus according to the present invention.
In FIG. 3, reference numeral 1 is a tuner, which carries out channel selection of the television wave inputted from the antenna 100 by the control from a microcomputer 14 . The television wave selected by the tuner 1 is converted into an intermediate frequency by a VIF (video intermediate frequency) circuit 2 and given to a video detector 3 . In the video detector 3 , the video signal is detected, and outputted to the first switching unit 5 after being amplified by the video amplifier 4 .
To first switching unit 5 , there are inputted an output of the above video amplifier 4 , an output of an OSD circuit 15 to be described later, and an output of a video output amplifier 19 for amplifying the video signal outputted by an Internet circuit 18 . The first switching unit 5 outputs one of video signals to a CRT (cathode ray tube) 6 under control of the microcomputer 14 .
Reference numeral 7 shows an SIF (sound intermediate frequency) circuit which detects an SIF signal from the output of the VIF circuit 2 and gives to a sound detector 8 . In the sound detector 8 , the sound signal is detected, and outputted to the second switching unit 10 after being amplified by sound amplifier 9 .
Second switching unit 10 , receives the output of the above sound amplifier 9 and an output of an sound output amplifier 20 for amplifying the sound signal outputted by the Internet circuit 18 to be described later. The second switching unit 10 outputs one of sound signals to a mixing circuit 11 by the control of the microcomputer 14 .
The output of the second switching unit 10 , as described above, and an output of a carrier amplifier 17 , as described later, are inputted to mixing circuit 11 , and both are mixed and output to a speaker 12 . Whereas the speaker 12 is shown in FIG. 3, there may be provided a headphone, earphone, etc. which generate audible sound instead of or in combination with speaker 12 .
Reference numeral 13 shows a remote control unit or an operating unit of the front panel of the television receiver 1 (both not shown). By operating it with user, various instructions can be given to the microcomputer 14 . The microcomputer 14 carries out various controls of the television receiver 1 according to the diversified instructions given from the outside by the user.
Reference numeral 15 shows the on-screen display circuit (hereinafter to be referred to as OSD circuit), which generates various on-screen character signals under control of the microcomputer 14 and outputs it to the first switching unit 5 as described above.
Reference numeral 16 is a modem, which is connected to a telephone line, and 17 is a carrier amplifier for amplifying the carrier sound from the modem 16 .
Reference numeral 18 shows the Internet circuit, which receives an information data of Internet given from the modem 16 and converts it to a video signal, and outputs sound signal. The video signal output from the Internet circuit 18 is amplified by the video output amplifier 19 and outputted to the first switching unit 5 . The sound signal outputted from the Internet circuit 18 is amplified by the sound output amplifier 20 and outputted to the second switching unit 10 .
Next, the operation of the television receiver as the Internet information displaying apparatus of the present invention as above will be explained.
At first, in viewing television broadcast, when the user operates the operating unit 13 to select the desired channel, a tuning voltage adapted to the selected channel is supplied to the tuner 1 from the microcomputer 14 . And, the television signal of the selected channel is inputted to the VIF circuit 2 , and the video signal is extracted by the video detector 3 and inputted to the video amplifier 4 . On the other hand, in the SIF circuit 7 , an SIF signal is detected from the output of the VIF circuit 2 , and further, in the sound detector 8 the sound signal is extracted and supplied to the sound amplifier 9 .
While the television broadcast is received, the television receiver outputs a video signal to the CRT 6 through connection of the first switching unit 5 to the video amplifier 4 by the microcomputer 14 . By connecting the second switching unit 10 to the sound amplifier 9 , the microcomputer 14 supplies a sound signal to the speaker 12 through the mixing circuit 11 . With respect to the sound signal, adjustment of the sound volume is feasible by controlling the sound amplifier 9 . This can be realized by the control of the sound amplifier 9 by the microcomputer 14 through operation of the operating unit 13 by the user.
On the other hand, in case the channel has been selected, the microcomputer 14 controls the OSD circuit 15 so as to generate a character signal to indicate the channel number. As a result, the character signal is outputted to the first switching unit 5 from the OSD circuit 15 . At this time, the microcomputer 14 controls so that the first switching unit 5 inputs the character signal outputted from the OSD circuit 15 and outputs it to the CRT 6 .
The OSD circuit 15 can carry out various displays of not only the channel character as described above but also the displays in connection with the sound volume adjustment, various adjustment modes, etc.
Next, with respect to the operation of the television receiver as an Internet information displaying apparatus of the present invention in the case of receiving Internet information, the operation is explained with reference to the flow chart of FIG. 4 A and FIG. 4 B.
At first, when the user operates the operating unit 13 to select an Internet connection mode (S 1 ), the microcomputer 14 controls the OSD circuit 15 so as to switch over the display from the screen of receiving the television broadcast to the Internet menu screen (to show various information menus such as traveling, stock, etc.). When the user operates the operating unit 13 to select the desired information from the menu screen (S 2 ), the microcomputer 14 transfers the data to the Internet circuit 18 , and the Internet circuit 18 causes the modem 16 to start connection of the telephone line with the provider (S 3 ). At this time, the microcomputer 14 changes over the menu screen to the television broadcast screen.
In case of not being the Internet connection mode, the screen continues receiving the television broadcast (S 10 ).
When the modem 16 connects the telephone line (connected with the provider), carrier sound is outputted from the modem 16 (S 4 ). Simultaneously with it, the information to indicate the start of connection of the telephone line is transmitted from the modem 16 to the Internet circuit 18 , and further the information is supplied to the microcomputer 14 .
On receipt of the information, the microcomputer 14 controls to lower the output level of the sound amplifier 9 for amplifying the sound signal of the television broadcast to a predetermined level. The sound signal whose sound volume has been lowered to a predetermined level by the sound amplifier 9 and the carrier sound outputted from the modem 16 are mixed by a mixing circuit 11 , given to the speaker 12 , and generated as audible sound (S 5 ). By such operation, due to the automatic lowering of the sound volume of television broadcast, the carrier sound of the modem 16 can be heard even when the user is viewing the television broadcast.
Furthermore, in order to allow the user to hear the carrier sound more clearly, the output level of the carrier amplifier 17 is simultaneously controlled by the microcomputer 14 to increase the level of the carrier sound, thereby making it possible for the user to hear the carrier sound of the modem 16 more clearly. And furthermore, it may be so arranged that, by setting the output level of the sound amplifier 9 to “0”, the sound signal of the television broadcast is muted to make only the carrier sound of the modem 16 outputted from the speaker 12 .
From the microcomputer 14 , a character signal indicating the fact of telephone line being connected is generated in the OSD circuit 15 and displayed by CRT 6 along with the television signal (S 6 ). With respect to the example of display in this case, a message 32 “Connection is in progress. Please wait for a while.” is displayed on the lower part of the screen 30 , as shown in the schematic diagram of FIG. 5 A. Alternatively, besides the message 32 , a timer 31 may be displayed to give indication of the connecting time. In addition, in carrying out sound volume adjustment, the change of the signal having the mixture of the carrier sound and the sound signal may be allowed for the user to recognize visually by bar display outputted from the OSD circuit 15 .
Further, when the telephone line is connected to the other party (provider), the data of the Internet information is received from the modem 16 , so that the information to indicate completion of connection of the telephone line is transmitted to the microcomputer 14 through the Internet circuit 18 (S 7 ).
By this operation, the microcomputer 14 controls the sound amplifier 9 and returns the sound volume of the television signal so as not to output the carrier sound (S 8 ). Further, as shown in the schematic diagram of FIG. 5B, by OSD circuit 15 , the connection time is displayed by the message 34 “Connection has been completed” and the display of the timer 33 (S 9 ).
In case of the connection with the Internet, the data from the modem 16 are received in the Internet circuit 18 and the video signal and sound signal are outputted. The video signal is supplied to the first switching unit 5 through the video output amplifier 19 , and the sound signal is supplied to the second switching unit 10 through the sound output amplifier 20 , by which the information of the Internet can be received through the CRT 6 and the speaker 12 .
In case the connection of the telephone line cannot be made in a predetermined time (no telephone line is connected) (S 11 ), the microcomputer 14 controls the sound amplifier 9 in a manner to return the sound volume of the sound signal of the television signal to the original state to prevent the carrier sound from being outputted (S 8 ). Furthermore, as shown in the schematic diagram of FIG. 5C, by the OSD circuit 15 , the connection time is displayed by the message 36 “Connection has failed” and the display of the timer 35 (S 9 ).
By the operation of the television receiver as an Internet information displaying apparatus of the present invention as above, the user can confirm the telephone line connection status by both sound and in a visual sense.
By the way, through speaker 12 , the connecting state of the telephone line is made audible not only in the carrier sound as described above but also in a sound of dialing (dial sound). The telephone line includes both a pulse dial type and a tone dial type, which respectively show different dial sounds. Of these, the pulse dial is a type to generate pulses by the switch which mechanically turns ON/OFF. Accordingly, when the dial sound is outputted from the speaker 12 , a problem occurs such that “pop noise” is generated to give unpleasant sound output.
In view of the above, in the second embodiment of the Internet information displaying apparatus of the present invention, the following countermeasures are taken to decrease the unpleasant sound. Hereinafter, explanation is given in reference to the flow chart of FIG. 6 and the time chart of FIG. 7 .
In this second embodiment, the constitution itself is the same as that of Embodiment 1 shown in FIG. 3 above, and the different portions are only a part of the software controls of the microcomputer 14 . Accordingly, in the following description, only the different portions are explained.
FIG. 6 is a flow chart showing the operation of the second embodiment. In the flow chart of the first embodiment shown in FIG. 4 A and FIG. 4B above, the step S 4 and the step S 5 are different, and in other steps the same operations are conducted, and therefore, the explanation on the part of the same operation is omitted.
At first, the operation until the modem 16 connects the telephone line with the provider (S 3 ) is the same as that of the first embodiment. When the telephone line is connected, the microcomputer 14 confirms whether the present telephone line is a pulse type or a tone type (S 100 ). In case of it being a pulse type, the microcomputer 14 confirms whether the present time is the period during which the modem 16 is generating the dial sound or not (dialing or not) (S 101 ).
As a result, when the time is a dial pulse generating period, the microcomputer 14 controls so that the sound volume of the dial sound of the telephone line becomes smaller (S 102 ). This dial sound is outputted by mixing with the sound signal of the television broadcast from the speaker 12 (S 103 ). This processing is continued for the period in which the dial sound is generated. When the dial pulse generating period elapses, the microcomputer 14 controls to make the sound volume of the dial sound of the telephone line larger (S 104 ). And, this dial sound of the telephone line and the sound signal of the television broadcast are mixed and outputted from the speaker 12 (S 105 ). Needless to say, it is allowable for the telephone line condition to be on-screen displayed.
In the meantime, in case the telephone line is a tone type, the step may be advanced from step S 100 to step S 104 and the dial sound directly outputted with enlarged sound volume or applied in the same manner as in the pulse type.
When the above condition is viewed by the time lapse, the condition becomes as in the time chart shown in FIG. 7 . Namely, according to the pulse type, during the non-connection with the Internet (a), the condition is somewhat muted, in the period of dialing the telephone line (b), the output sound volume of the modem 6 is small, in the period (c) which is the communication stage with the provider, the output sound volume of the modem 16 becomes large, and in the Internet connected period (d), it is muted. On the other hand, in the tone type, in the period of dialing the telephone line (b) and the period of communication with a provider, the output sound volume of the modem 6 is enlarged.
According to the second embodiment as above, the unpleasant pop noise caused by the pulse type dial sound can be decreased.
Besides the embodiments mentioned above, there may be the third embodiment whose constitution example is shown in the block diagram of FIG. 8 .
In the block diagram shown in FIG. 8, a DSP (digital signal processor) 37 is added to the constitution of the first embodiment to generate pseudo sound. The DSP 37 may be that built in the modem, or that additionally provided as a extra circuit.
Hereinafter, based on the block diagram of FIG. 8 and the flow chart of FIG. 9, the operation of the third embodiment is explained.
However, in the flow chart shown in FIG. 9 of the third embodiment, the only point of change is that the step S 102 shown in the flow chart of FIG. 6 in the second embodiment as described above is changed to the step 106 which generates the pseudo tone, and other operations are unchanged.
Accordingly, in case the telephone line is a pulse type and dial sound is generated, in the dial pulse generating period, under control of the microcomputer 14 , DSP 37 generates the sound simulating dial sound like “pip-pop-pa” in a tone type and outputs it to the speaker 12 . At this time, the actually generated dial sound is controlled so as not to be outputted under control of the carrier amplifier 17 by the microcomputer 14 . As to this pseudo tone, it may be so arranged as to output tone type sound corresponding to the pulse type sound, or a completely different sound as desired.
As described in detail above, according to the third embodiment of the present invention, even in a case where the user is viewing a television broadcast, the connection operation condition of the telephone line can be confirmed by the dial sound.
By the way, in an ordinary television receiver, it is not the case for all the video signals received as television broadcast to be displayed but only the range called an effective scanning region in horizontal direction is displayed on the CRT 6 . Namely, the period for scanning in horizontal direction is 63.5 μs of which the video signal is in the period of 54.6 μs. In a television receiver, display is made only for about 49 μs of the period (to be called an effective scanning line region) excluding the period of 5% at both ends of the video signal period (over-scanning region).
On the other hand, in the Internet information, due to the display of characters and pictures over full screen areas, when the images are converted into video signals, they are formed as video signals including an over-scan region, as previously mentioned. Accordingly, there is a problem that partial characters and picture images in the original Internet information come into the overscan region to make the screen image invisible with a television receiver (ref. FIG. 10 B).
In order to prevent such a phenomenon, the Internet displaying apparatus of the present invention is designed in the following manner. Namely, in order to display the Internet information on the CRT 6 of a television receiver in the same manner as for displaying on a monitor for a personal computer, it may be arranged to make display on a screen of 640 dots in the horizontal direction and 480 dots in the vertical direction. To the convenience, because the number of the effective scanning lines in the vertical direction of the television receiver is 480, this can be easily realized. In order to obtain such screen size, the 640 dots in the horizontal direction may be met by the video signal region of one clock (0.07 μs)×640=44.8 μs because one clock is 14.3 MHz. This comes within the effective horizontal scanning line region of 49 μs which means that all the Internet information is to be displayed (ref. FIG. 10 A).
By the way, when display is made as described above, the discontinued points of the video signals are also to be displayed, in which case the right and left periods having no video signal are set to black levels. However, as the video signal level shows sharp changes at the border line between the video signal and the black level, voltage fluctuation occurs in the high voltage circuit.
Here, explanation is made on the voltage fluctuation of the high voltage circuit. When a video signal level is developed suddenly from the black level, though no beam current of CRT 6 runs on a black level, on generation of a video signal, the beam current naturally flows out. And, as a high voltage is supplied to the CRT 6 from the high voltage circuit, the high voltage changes due to the flow of the beam current. This high voltage circuit is supplied from the fly back transformer (FBT), and a deflection operation in the horizontal direction is to be made from the FBT. Accordingly, when the high voltage fluctuates, the deflection current in the horizontal deflection also changes, in other words, the amplitude changes, with the result that the size of the picture image in the horizontal direction (lateral direction) changes to give bend of picture images (ref. FIG. 10 A). Especially, such a defect is remarkable at the boundary of the video signals.
In a wide television receiver having an aspect ratio of 16:9, for example, the screen may be displayed in division into two areas. Concretely, there may be arranged to display a video signal of television broadcast on one screen, and a video signal of the Internet on the other screen. Even in such a case, it may be so arranged for the video signal obtained from the Internet information to be displayed with addition of the white level on the right and left boundaries as described above.
In view of the situation as mentioned above, the Internet information displaying apparatus of the present invention has also a function to make the boundary of the screen in which the Internet information is displayed less conspicuous. Hereinafter, the fourth embodiment of the Internet information displaying apparatus of the present invention having such function is concretely explained.
FIG. 11 is a block diagram showing an example of constitution of the fourth embodiment, which is made by remodelling a part of the block diagram of FIG. 3 which shows the constitution of the first embodiment. Namely, in the block diagram shown in FIG. 3, the video signal outputted from the Internet circuit 18 is directly inputted to the video output amplifier 19 , but in this fourth embodiment, a switch 21 is provided between the Internet circuit 18 and the video amplifier 19 . This switch 21 is connected at one input end to the level setting volume 23 , and at the other input end to the Internet circuit 18 , with the output end connected to the video amplifier 19 . And, by an output (switching signal) of the two input logic (OR) circuits 22 , the switch 21 is controlled. To one input of the logic circuit 22 is inputted a BLK pulse from the Internet circuit 18 , and to the other input an HBLK pulse is inputted from the non-illustrated horizontal deflection circuit, respectively.
The constitution of other portions is the same as that of the first embodiment shown in FIG. 3 .
Next, the operation of this fourth embodiment is explained with reference to the time chart of FIG. 12 .
When a telephone line is connected and the Internet information is sent to the Internet circuit 18 through the modem 18 , the Internet circuit 18 converts the Internet information (digital data) into a video signal and outputs it to the switch 21 .
Also, to the other input end of the switch 21 , a DC level which has been adjusted by the level setting volume 23 is inputted. This DC level is set so that the white level of the video signal becomes 30%-50%.
On the other hand, from the Internet circuit 18 , there is outputted as shown by (b) in FIG. 12, the blanking (BLK) pulse corresponding to the converted video signal period which is shown by (a) in FIG. 12 . Also, the horizontal blanking (HBLK) pulse as shown by (c) in FIG. 12 for blanking the preceding and succeeding periods of the horizontal synchronizing signal is formed in the non-illustrated horizontal deflection circuit. The BLK pulse and HBLK pulse are inputted to the logic circuit 22 , where a switching signal for switching the switch 21 as shown by (b) in FIG. 12 is outputted.
Accordingly, when the switch 21 is controlled by the switching signal which is an output signal of the logic circuit 22 , the switch 21 outputs the video signal from the Internet circuit 18 to the video output amplifier 19 for the period in which the switching signal is “H”, and switches the white level set by the level setting volume 23 to output to the video output amplifier 19 during the period in which the switching signal is “L”. By this operation, there is supplied to the video output amplifier 19 from the switch 21 a DC level voltage in which a white level is set to a video signal as shown by (e) in FIG. 12 .
The output from the video output amplifier 21 is outputted to the CRT 6 and displayed as described above. Accordingly, as shown in the above FIG. 10C, the right and left portions of the video signal are displayed as the predetermined white level (gray color), and the boundary with the video signal becomes less conspicuous.
As described above, according to the fourth embodiment, bending of picture images at the boundary between the video signal and the right and left blanking periods can be prevented, and the boundary thereof becomes less remarkable.
In the foregoing embodiments, description is made on the cases of the Internet information displaying apparatus of the present invention being applied to the television receiver, but the application is not limited to it. For example, reverse to the above embodiment, the Internet information display may be realized by incorporating a function as a television receiver on an ordinary personal computer with which Internet communication is feasible.
As this invention may be embodied in several forms without departing from the spirit of essential characteristics thereof, the present embodiments is therefore illustrative and not restrictive, since the scope of the invention is defined by the appended claims rather than by the description preceding them, and all changes that fall within metes and bounds of the claims, or equivalence of such metes and bounds thereof are therefore intended to be embraced by the claims.
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An Internet information displaying apparatus, comprises an SIF ( 7 ) for outputting a video signal by extracting from the television signal received by a tuner ( 1 ); a speaker ( 12 ) for generating the sound signal as audible sound; modem ( 16 ) for transmitting and receiving the digital data through a telephone line by converting the digital data into a carrier signal by sound in transmitting, and by demodulating the carrier signal by sound into digital data at receiving; carrier amplifier ( 17 ) for outputting the carrier signal by the transmitting/receiving sound of the modem ( 16 ); and mixing circuit ( 11 ) for giving sound signal generated in the telephone line to the speaker ( 12 ) and generating as audible sound. Even when a television signal is being received and the sound is outputted from the speaker, the connection condition by telephone line is easily recognizable.
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[0001] This Non-Provisional application is a Continuation of and claims the benefit of priority from U.S. patent application Ser. No. 13/849,137, filed Mar. 22, 2013 and Provisional Patent Application No. 61/614,273 filed Mar. 22, 2012, the entire disclosures of which are incorporated by reference herein.
FIELD OF THE INVENTION
[0002] The present invention relates generally to archery sights. More specifically, the present invention relates to an archery sight with at least one adjustable sight pin and a plurality of fixed sight pins.
BACKGROUND
[0003] There currently exist various sighting devices for aiding a user of an archery bow when attempting to strike a given target with an arrow. Examples of such devices include: U.S. Pat. No. 7,574,810 to LoRocco, U.S. Pat. No. 7,331,112 to Gibbs, U.S. Pat. No. 7,278,216 to Grace, U.S. Pat. No. 5,630,279 to Slates, U.S. Pat. No. 7,401,411 to White, and U.S. Pat. No. 4,846,141 to Johnson, all of which are incorporated by reference herein in their entireties.
SUMMARY OF THE INVENTION
[0004] The present invention contemplates a novel system, device, and methods for an archery sight comprising at least one adjustable pin and at least one fixed pin.
[0005] In one embodiment, an archery sight for interconnection with a bow is provided, the archery sight comprising a first substantially rigid member comprising a first sighting pin, the first sighting pin being selectively positionable by a user in at least a vertical direction, a second member comprising a plurality of sighting pins, the plurality of sighting pins being substantially fixed in a vertical position and adjustable with respect to each other, and the second member interconnected to the first substantially rigid member, the first substantially rigid member and the second member being selectively positionable with respect to one another between a first position and a second position. Both the first sighting pin and plurality of sighting pins may also be adjustable in a horizontal plane to adjust for windage as necessary.
[0006] The present disclosure contemplates a wide variety of means for securing a portion of a sight in various positions. For example, various magnetic securing members, clasps, hooks, shelves, vertical supports, pins and similar features are contemplated.
[0007] As referred to herein, bow sights may comprise any number of known devices including, but not limited to, pin sights, dot sights, fiber optic sights, and various other known archery sights as will be recognized by one of skill in the art and comprising at least one sighting pin.
[0008] In one embodiment, a method of adjusting an archery sight for a bow is provided, the archery sight comprising a first pin adjustable in a vertical direction and a plurality of substantially fixed pins, the method comprising determining a corresponding distance of travel of a projectile for at least one of the plurality of substantially fixed pins by targeting an object at a known distance (e.g. a shooting range target), and based on the determined corresponding distance of travel for the projectile for the at least one substantially fixed pin, selectively adjusting the first pin with respect to the at least one of plurality of substantially fixed pins such that the first pin corresponds to a second distance, and selectively and substantially removing the plurality of substantially fixed pins from an archer's line of sight, such that the archer may then target and shoot objects with a minimal amount of sight pins in the archer's vision.
[0009] In certain embodiments, one or more sight pins are provided as projected or virtual sight pins. For example, a plurality of electronic sight pins may be provided on a sighting or viewing screen. Such a screen is rotatable or removable from view, at least in embodiments where the virtual pins comprise the “fixed” sight pins disclosed herein. In various embodiments, secondary sighting pins may be vertically adjustable with respect to one another, and adapted to be moved, pivoted, swung, translated, etc. out of a field of view, thus leaving only a single primary adjustable sight pin in a user's field of view.
[0010] The Summary of the Invention is neither intended nor should it be construed as being representative of the full extent and scope of the present disclosure. The present disclosure is set forth in various levels of detail in the Summary of the Invention as well as in the attached drawings and the Detailed Description of the Invention and no limitation as to the scope of the present disclosure is intended by either the inclusion or non-inclusion of elements, components, etc. in this Summary of the Invention. Additional aspects of the present disclosure will become more readily apparent from the Detailed Description, particularly when taken together with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] Those of skill in the art will recognize that the following description is merely illustrative of the principles of the disclosure, which may be applied in various ways to provide many different alternative embodiments. This description is made for illustrating the general principles of the teachings of this disclosure invention and is not meant to limit the inventive concepts disclosed herein.
[0012] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate embodiments of the disclosure and together with the general description of the disclosure given above and the detailed description of the drawings given below, serve to explain the principles of the disclosures.
[0013] It should be understood that the drawings are not necessarily to scale. In certain instances, details that are not necessary for an understanding of the disclosure or that render other details difficult to perceive may have been omitted. It should be understood, of course, that the disclosure is not necessarily limited to the particular embodiments illustrated herein.
[0014] FIG. 1 is an elevation view of an adjustable archery sight according to one embodiment of the present disclosure;
[0015] FIG. 2 is an elevation view of an adjustable archery sight according to one embodiment of the present disclosure;
[0016] FIG. 3 is an elevation view of an adjustable archery sight according to one embodiment of the present disclosure;
[0017] FIG. 4 is an elevation view of an adjustable archery sight according to one embodiment of the present disclosure;
[0018] FIG. 5 is an elevation view of an adjustable archery sight according to one embodiment of the present disclosure;
[0019] FIG. 6 is an elevation view of an adjustable archery sight according to one embodiment of the present disclosure; and
[0020] FIG. 7 is an elevation view of an adjustable archery sight according to one embodiment of the present disclosure.
DETAILED DESCRIPTION
[0021] The present invention has significant benefits across a broad spectrum of endeavors. To acquaint persons skilled in the pertinent arts most closely related to the present invention, a preferred embodiment of the method that illustrates the best mode now contemplated for putting the invention into practice is described herein by, and with reference to, the annexed drawings that form a part of the specification. The exemplary method is described in detail without attempting to describe all of the various forms and modifications in which the invention might be embodied. As such, the embodiments described herein are illustrative, and as will become apparent to those skilled in the arts, can be modified in numerous ways within the scope and spirit of the invention.
[0022] Referring now to FIGS. 1-7 , an archery sight according to various embodiments of the present disclosure is shown. It should be understood that the drawings are not necessarily to scale. In certain instances, details that are not necessary for an understanding of the invention or that render other details difficult to perceive may have been omitted from these drawings. It should be understood, of course, that the invention is not limited to the particular embodiments illustrated in the drawings.
[0023] Referring now to FIG. 1 , an embodiment of an archery sight 2 according to the present disclosure is shown. The archery sight 2 is mountable to any number of bows and/or bow risers. The sight comprises at least one rotational adjustment member 6 a , 6 b for vertical and horizontal adjustment and two frame portions 8 a , 8 b , at least one of the frame portions 8 a , 8 b being rotatable or otherwise moved out of an archer's line of sight to a target, with respect to the other frame portion or the bow. An adjustable sighting pin 12 is provided on one frame member 8 a and a plurality of fixed sighting pins 10 are provided on another frame member 8 b . Fixed sighting pins 10 , as will be recognized by one of ordinary skill in the art, comprise substantially rigid elongate points, the vertical position of which correspond to a predetermined down-field range. A lower sighting pin 10 corresponds to a first travel distance of a projectile, where pins located vertically above that lower pin correspond to progressively shorter travel distances for a projectile. Horizontal or windage adjustments can also typically be made on the fixed sight pins as necessary.
[0024] Frame member 8 b is rotatable with respect to first frame member 8 a about a vertical axis of rotation 18 . FIG. 1 depicts frame member 8 b in a generally open position. When first 8 a and second 8 b frame members are placed in a closed position, internal surface portion 20 a of first member 8 a and internal surface member 20 b of second member 8 b will positioned proximal to one another in a substantially parallel manner. Portions of internal surfaces 20 a , 20 b may, but need not necessarily be, in direct contact with one another.
[0025] Thus, embodiments of the present disclosure contemplate an archery sight 2 with a plurality of fixed sight pins 10 and at least one adjustable sight pin 12 , wherein the special relationship between the fixed pins 10 and the adjustable pin 12 is variable. One advantage of this advancement is that when the sight 2 is placed in a closed position, adjustable pin 12 may be moved with reference to the fixed pins 10 for a predetermined distance, as fixed pins 10 will be disposed generally parallel and proximal to the sight pin. Furthermore, when a user desires to remove the fixed pins 10 from a direct field of view, the second frame portion 8 b and interconnected fixed pins 10 are moved out of view by rotation, completive removal (e.g. by magnets), moved transversely, or otherwise positioned out of a field of view.
[0026] Second frame member 8 b may be at least partially secured to the first frame member 8 a in a variety of ways. For example, at least portions of the frame members 8 a , 8 b may comprise magnetic properties whereby the members 8 a , 8 b are magnetically secured when provided in a closed position. Similarly, magnetic materials may be provided to secure a second frame member 8 b in an open position. For example, magnetic materials may be provided on the first 8 a and/or second 8 b members proximal hinges 16 and on a surface perpendicular to the internal surfaces 20 a , 20 b.
[0027] In various embodiments, one or more latches are provided to selectively connect the frame member portions 8 a , 8 b . Latches comprise, for example, spring latches, slam latches, cam locks, Norfolk latches, Suffolk latches, crossbars, cabin hooks and other latches as will be recognized by one of skill in the art.
[0028] In certain embodiments, one or more hinge members connecting portions of the sight comprise self-locking features, such as a toothed or ratcheted hinge capable of generally securing the position of the rotatable member at a plurality of relatively narrow-spaced intervals.
[0029] In various embodiments, magnetic features are provided on at least one frame member. In one embodiment, for example, a hinged member is magnetically fastenable to a stationary member with a sufficient magnetic force to prevent undesired swinging or opening of the hinged member, yet still allows a user to easily open and/or rotate the hinged member. Magnetic features may be employed to secure hinged features in open positions and closed positions.
[0030] The individual pins, in various embodiments, are pushed out of sight with a ball détente, thus obviating the need for a second frame portion.
[0031] Various additional features common to archery sights may be provided in combination with features of the present disclosure. For example, a bubble level 14 for leveling a bow in at least one axis is provided on at least one of the first 8 a and second 8 b frame members of the sight 2 . As used herein, the term “vertical” generally refers to vertical with respect to the force vector of gravity, and relates to the position of a bow when aimed or held upright and angle at approximately 0 degrees with respect to a horizon.
[0032] FIG. 2 depicts an archery sight 2 according to one embodiment of the present disclosure. As shown in FIG. 2 , an archery sight 2 is provided of similar construction to the sight shown and described in FIG. 1 . The sight of FIG. 2 , however, comprises a second frame portion 20 b that is rotatable with respect to a first frame portion 20 a about an axis 22 that is disposed substantially perpendicular to the axis 18 of FIG. 1 . Thus, a portion of the sight 2 of FIG. 2 is hingedly rotated upwardly or downwardly in order to move a set of fixed pins 10 out of the line of sight of an archer. Portions of the sight 2 may be rotated about one or more hinges 24 and secured in any manner as shown and described herein. The second frame member 20 b may be secured in an open position by a magnetic force between at least a portion of the frame member 20 b and a portion of the bow riser or the bow.
[0033] FIG. 3 is an elevation view of one embodiment of the present disclosure. An archery sight 2 is provided with a rotatable frame member 26 , the rotatable frame member 26 comprising a plurality of fixed sight pins 10 . The frame member 26 is rotatable with respect to a fixed member 28 provided with a slot 29 defining a path of travel for an adjustable pin 32 . The adjustable pin is positioned on an adjustable carriage 30 , further comprising a bubble level 14 . Fixed member 28 comprises a generally planar structure and is hingedly connected to rotatable member 26 .
[0034] FIG. 4 is a front elevation view of another embodiment of the present disclosure. A sight 2 is provided for interconnection a bow or portion of a bow. The sight 2 comprises a substantially stationary member 36 comprising an adjustable sighting pin 12 that is translatable in at least a vertical direction. A hinged member 34 is hingedly connected to the member 36 and rotatable about a substantially vertical axis 18 . The hinged member 34 comprises a plurality of sighting pins 10 , the sighting pins being movable into and out of a line of sight further comprising the adjustable pin 12 .
[0035] FIG. 5 is a front elevation view of another embodiment of the present disclosure. A sight 2 is provided for interconnection a bow or portion of a bow. The sight 2 comprises a substantially stationary member 36 comprising an adjustable sighting pin 12 that is translatable in at least a vertical direction. A hinged member 38 is hingedly connected to the member 36 and rotatable about a substantially horizontal axis 40 . The hinged member 38 comprises a plurality of sighting pins 10 , the sighting pins being movable into and out of a line of sight further comprising the adjustable pin 12 .
[0036] FIG. 6 is a front elevation view of another embodiment of the present disclosure. A sight 2 is provided for interconnection a bow or portion of a bow. The sight 2 comprises a substantially stationary member 36 comprising an adjustable sighting pin 12 that is translatable in at least a vertical direction. A translatable carriage member 42 is connected to the member 36 . In one embodiment, the carriage member 42 is translatable in a lateral direction 46 and along track 44 , such that interconnected sighting pins 10 may be moved in and out of a combined line of sight with an adjustable pin 12 . Although FIG. 6 depicts a carriage 42 that is translatable in a lateral direction 46 , it will be expressly recognized that various features of the present disclosure may be provided as translatable in any number of directions including, for example, horizontal directions, vertical directions, and diagonal translations, about any number of axis or planes.
[0037] FIG. 7 is a front perspective view of another embodiment of the present disclosure. A sight 2 is provided for interconnection a bow or portion of a bow. The sight 2 comprises a first frame member 54 a comprising an adjustable sighting pin 12 that is translatable in at least a vertical direction. A second frame member 54 b is hingedly connected to the member 54 a and rotatable about a substantially horizontal axis 48 . The hinged member 54 b comprises a plurality of fixed sighting pins 10 , the sighting pins being movable into and out of a line of sight further comprising the adjustable pin 12 . As shown, the second frame member 54 b is rotatable either clockwise or counterclockwise, such that an outer surface portion 52 of the member 54 b remains outwardly-facing.
[0038] Frame member 54 b may be secured in various positions by various means, as will be recognized by one of ordinary skill in the art. For example, frame member 54 b may be rotated and “clicked” or locked into a closed position with the aid of the combination of a male and female member. A frame member 54 a , 54 b in such an embodiment comprises a hemispherical projection which locks into and mates with a female receiving portion on the other member. A ledge or other rotational delimiting is provided to prevent over-rotation of frame member 54 b and maintain the member 54 b substantially in the position shown in FIG. 7 .
[0039] While various embodiments of the present invention have been described in detail, it is apparent that modifications and alterations of those embodiments will occur to those skilled in the art. However, it is to be expressly understood that such modifications and alterations are within the scope and spirit of the present invention. Further, the invention(s) described herein are capable of other embodiments and of being practiced or of being carried out in various ways. In addition, it is to be understood that the phraseology and terminology used herein is for the purposes of description and should not be regarded as limiting. The use of “including,” “comprising,” or “adding” and variations thereof herein are meant to encompass the items listed thereafter and equivalents thereof, as well as, additional items.
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An archery sight for a bow is provided. The sight provides at least one sight pin that is adjustable, such as a sliding pin adjustable in a vertical direction, and a plurality of fixed sight pins. The plurality of sight pins are repositionable such that they may either be placed in alignment with the adjustable sight pin or moved out of the way so as avoid obstructing an archer's target or vision.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of co-pending application Ser. No. 11/042,281, filed on Jan. 24, 2005, which is a divisional of application Ser. No. 10/259,139, filed on Sep. 9, 2002, which is a continuation-in-part of co-pending application Ser. No. 10/123,389, filed on Apr. 16, 2002, which claims the benefit of provisional application Ser. No. 60/284,465 filed on Apr. 18, 2001, which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates to novel arylindenopyridines and their therapeutic and prophylactic uses. Disorders treated and/or prevented using these compounds include neurodegenerative and movement disorders ameliorated by antagonizing Adenosine A2a receptors and inflammatory and AIDS-related disorders ameliorated by inhibiting phosphodiesterace activity.
BACKGROUND OF THE INVENTION
[0000] Adenosine A2a Receptors
[0003] Adenosine is a purine nucleotide produced by all metabolically active cells within the body. Adenosine exerts its effects via four subtypes of cell-surface receptors (A1, A2a, A2b and A3), which belong to the G protein coupled receptor superfamily (Stiles, G. L. Journal of Biological Chemistry, 1992, 267, 6451). A1 and A3 couple to inhibitory G protein, while A2a and A2b couple to stimulatory G protein. A2a receptors are mainly found in the brain, both in neurons and glial cells (highest level in the striatum and nucleus accumbens, moderate to high level in olfactory tubercle, hypothalamus, and hippocampus etc. regions) (Rosin, D. L.; Robeva, A.; Woodard, R. L.; Guyenet, P. G.; Linden, J. Journal of Comparative Neurology, 1998, 401, 163).
[0004] In peripheral tissues, A2a receptors are found in platelets, neutrophils, vascular smooth muscle and endothelium (Gessi, S.; Varani, K.; Merighi, S.; Ongini, E.; Borea, P. A. British Journal of Pharmacology, 2000, 129, 2). The striatum is the main brain region for the regulation of motor activity, particularly through its innervation from dopaminergic neurons originating in the substantia nigra. The striatum is the major target of the dopaminergic neuron degeneration in patients with Parkinson's Disease (PD). Within the striatum, A2a receptors are co-localized with dopamine D2 receptors, suggesting an important site of for the integration of adenosine and dopamine signaling in the brain (Fink, J. S.; Weaver, D. R.; Rivkees, S. A.; Peterfreund, R. A.; Pollack, A. E.; Adler, E. M.; Reppert, S. M. Brain Research Molecular Brain Research, 1992, 14,186).
[0005] Neurochemical studies have shown that activation of A2a receptors reduces the binding affinity of D2 agonist to their receptors. This D2R and A2aR receptor-receptor interaction has been demonstrated in striatal membrane preparations of rats (Ferre, S.; von Euler, G.; Johansson, B.; Fredholm, B. B.; Fuxe, K. Proceedings of the National Academy of Sciences of the United States of America, 1991, 88, 7238) as well as in fibroblast cell lines after transfected with A2aR and D2R cDNAs (Salim, H.; Ferre, S.; Dalal, A.; Peterfreund, R. A.; Fuxe, K.; Vincent, J. D.; Lledo, P. M. Journal of Neurochemistry, 2000, 74, 432). In vivo, pharmacological blockade of A2a receptors using A2a antagonist leads to beneficial effects in dopaminergic neurotoxin MPTP(1-methyl-4-pheny-l,2,3,6-tetrahydropyridine)-induced PD in various species, including mice, rats, and monkeys (Ikeda, K.; Kurokawa, M.; Aoyama, S.; Kuwana, Y. Journal of Neurochemistry, 2002, 80, 262). Furthermore, A2a knockout mice with genetic blockade of A2a function have been found to be less sensitive to motor impairment and neurochemical changes when they were exposed to neurotoxin MPTP (Chen, J. F.; Xu, K.; Petzer, J. P.; Staal, R.; Xu, Y. H.; Beilstein, M.; Sonsalla, P. K.; Castagnoli, K.; Castagnoli, N., Jr.; Schwarzschild, M. A. Journal of Neuroscience, 2001, 21, RC143).
[0006] In humans, the adenosine receptor antagonist theophylline has been found to produce beneficial effects in PD patients (Mally, J.; Stone, T. W. Journal of the Neurological Sciences, 1995, 132, 129). Consistently, recent epidemiological study has shown that high caffeine consumption makes people less likely to develop PD (Ascherio, A.; Zhang, S. M.; Hernan, M. A.; Kawachi, I.; Colditz, G. A.; Speizer, F. E.; Willett, W. C. Annals of Neurology, 2001, 50, 56). In summary, adenosine A2a receptor blockers may provide a new class of antiparkinsonian agents (Impagnatiello, F.; Bastia, E.; Ongini, E.; Monopoli, A. Emerging Therapeutic Targets, 2000, 4, 635).
[0000] Phosphodiesterase Inhibitors
[0007] There are eleven known families of phosphodiesterases (PDE) widely distributed in many cell types and tissues. In their nomenclature, the number indicating the family is followed by a capital letter that indicates a distinct gene. A PDE inhibitor increases the concentration of cAMP in tissue cells, and hence, is useful in the prophylaxis or treatment of various diseases caused by the decrease in cAMP level which is induced by the abnormal metabolism of cAMP. These diseases include conditions such as hypersensitivity, allergy, arthritis, asthma, bee sting, animal bite, bronchospasm, dysmenorrhea, esophageal spasm, glaucoma, premature labor, a urinary tract disorder, inflammatory bowel disease, stroke, erectile dysfunction, HIV/AIDS, cardiovascular disease, gastrointestinal motility disorder, and psoriasis.
[0008] Among known phosphodiesterases today, PDE1 family are activated by calcium-calmodulin; its members include PDE1A and PDE1B, which preferentially hydrolyze cGMP, and PDE1C which exhibits a high affinity for both cAMP and cGMP. PDE2 family is characterized as being specifically stimulated by cGMP. PDE2A is specifically inhibited by erythro-9-(2-hydroxy-3-nonyl)adenine (EHNA). Enzymes in the PDE3 family (e.g. PDE3A, PDE3B) are specifically inhibited by cGMP. PDE4 (e.g. PDE4A, PDE4B, PDE4C, PDE4D) is a cAMP specific PDE present in T-cells, which is involved in inflammatory responses. A PDE3 and/or PDE4 inhibitor would be predicted to have utility in the following disorders: autoimmune disorders (e.g. arthritis), inflammatory bowel disease, bronchial disorders (e.g. asthma), HIV/AIDS, and psoriasis. A PDE5 (e.g. PDE5A) inhibitor would be useful for the treatment of the following disorders: cardiovascular disease and erectile dysfunction. The photoreceptor PDE6 (e.g. PDE6A, PDE6B, PDE6C) enzymes specifically hydrolyze cGMP. PDE8 family exhibits high affinity for hydrolysis of both cAMP and cGMP but relatively low sensitivity to enzyme inhibitors specific for other PDE families.
[0009] Phosphodiesterase 7 (PDE7A, PDE7B) is a cyclic nucleotide phosphodiesterase that is specific for cyclic adenosine monophosphate (cAMP). PDE7 catalyzes the conversion of cAMP to adenosine monophosphate (AMP) by hydrolyzing the 3′-phosphodiester bond of cAMP. By regulating this conversion, PDE7 allows for non-uniform intracellular distribution of cAMP and thus controls the activation of distinct kinase signalling pathways. PDE7A is primarily expressed in T-cells, and it has been shown that induction of PDE7A is required for T-cell activation (Li, L.; Yee, C.; Beavo, J. A. Science 1999, 283, 848). Since PDE7A activation is necessary for T-cell activation, small molecule inhibitors of PDE7 would be useful as immunosuppressants. An inhibitor of PDE7A would be predicted to have immunosuppressive effects with utility in therapeutic areas such as organ transplantation, autoimmune disorders (e.g. arthritis), HIV/AIDS, inflammatory bowel disease, asthma, allergies and psoriasis.
[0010] Few potent inhibitors of PDE7 have been reported. Most inhibitors of other phosphodiesterases have IC 50 's for PDE7 in the 100 μM range. Recently, Martinez, et al. ( J. Med. Chem. 2000, 43, 683) reported a series of PDE7 inhibitors, among which the two best compounds have PDE7 IC 50 's of 8 and 13 μM. However, these compounds were only 2-3 times selective for PDE7 over PDE4 and PDE3.
[0011] Finally, the following compounds have been disclosed, and some of them are reported to show antimicrobial activity against strains such as Plasmodium falciparum, Candida albicans and Staphylococcus aureus (Gorlitzer, K.; Herbig, S.; Walter, R. D. Pharmazie 1997, 504):
SUMMARY OF THE INVENTION
[0012] This invention provides a compound having the structure of Formula I
or a pharmaceutically acceptable salt thereof, wherein
(a) R 1 is selected from the group consisting of:
(i) —COR 5 , wherein R 5 is selected from H, optionally substituted C 1-8 straight or branched chain alkyl, optionally substituted aryl and optionally substituted arylalkyl;
wherein the substituents on the alkyl, aryl and arylalkyl group are selected from C 1-8 alkoxy, phenylacetyloxy, hydroxy, halogen, p-tosyloxy, mesyloxy, amino, cyano, carboalkoxy, or NR 20 R 21 wherein R 20 and R 21 are independently selected from the group consisting of hydrogen, C 1-8 straight or branched chain alkyl, C 3-7 cycloalkyl, benzyl, aryl, or heteroaryl or NR 20 R 21 taken together form a heterocycle or heteroaryl;
(ii) COOR 6 , wherein R 6 is selected from H, optionally substituted C 1-8 straight or branched chain alkyl, optionally substituted aryl and optionally substituted arylalkyl;
wherein the substituents on the alkyl, aryl and arylalkyl group are selected from C 1-8 alkoxy, phenylacetyloxy, hydroxy, halogen, p-tosyloxy, mesyloxy, amino, cyano, carboalkoxy, or NR 20 R 21 wherein R 20 and R 21 are independently selected from the group consisting of hydrogen, C 1-8 straight or branched chain alkyl, C 3-7 cycloalkyl, benzyl, aryl, or heteroaryl or NR 20 R 21 taken together form a heterocycle or heteroaryl;
(iii) cyano; (iv) a lactone or lactam formed with R 4 ; (v) —CONR 7 R 8 wherein R 7 and R 8 are independently selected from H, C 1-8 straight or branched chain alkyl, C 3-7 cycloalkyl, trifluoromethyl, hydroxy, alkoxy, acyl, alkylcarbonyl, carboxyl, arylalkyl, aryl, heteroaryl and heterocyclyl;
wherein the alkyl, cycloalkyl, alkoxy, acyl, alkylcarbonyl, carboxyl, arylalkyl, aryl, heteroaryl and heterocyclyl groups may be substituted with carboxyl, alkyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, hydroxamic acid, sulfonamide, sulfonyl, hydroxy, thiol, alkoxy or arylalkyl, or R 7 and R 8 taken together with the nitrogen to which they are attached form a heterocycle or heteroaryl group;
(vi) a carboxylic ester or carboxylic acid bioisostere including optionally substituted heteroaryl groups
(b) R 2 is selected from the group consisting of optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl and optionally substituted C 3-7 cycloalkyl; (c) R 3 is from one to four groups independently selected from the group consisting of:
(i) hydrogen, halo, C 1-8 straight or branched chain alkyl, arylalkyl, C 3-7 cycloalkyl, C 1-8 alkoxy, cyano, C 1-4 carboalkoxy, trifluoromethyl, C 1-8 alkylsulfonyl, halogen, nitro, hydroxy, trifluoromethoxy, C 1-8 carboxylate, aryl, heteroaryl, and heterocyclyl; (ii) —NR 10 R 11 wherein R 10 and R 11 are independently selected from H, C 1-8 straight or branched chain alkyl, arylalkyl, C 3-7 cycloalkyl, carboxyalkyl, aryl, heteroaryl, and heterocyclyl or R 10 and R 11 taken together with the nitrogen form a heteroaryl or heterocyclyl group; (iii) —NR 12 COR 13 wherein R 12 is selected from hydrogen or alkyl and R 13 is selected from hydrogen, alkyl, substituted alkyl, C 1-3 alkoxyl, carboxyalkyl, R 30 R 31 N(CH 2 ) p —, R 30 R 31 NCO(CH 2 ) p —, aryl, arylalkyl, heteroaryl and heterocyclyl or R 12 and R 13 taken together with the carbonyl form a carbonyl containing heterocyclyl group,
wherein, R 30 and R 31 are independently selected from H, OH, alkyl, and alkoxy, and p is an integer from 1-6, wherein the alkyl group may be substituted with carboxyl, alkyl, aryl, substituted aryl, heterocyclyl, substituted heterocyclyl, heteroaryl, substituted heteroaryl, hydroxamic acid, sulfonamide, sulfonyl, hydroxy, thiol, alkoxy or arylalkyl;
(d) R 4 is selected from the group consisting of (i) hydrogen, (ii) C 1-3 straight or branched chain alkyl, (iii) benzyl and (iv) —NR 13 R 14 ,
wherein R 13 and R 14 are independently selected from hydrogen and C 1-6 alkyl; wherein the C 1-3 alkyl and benzyl groups are optionally substituted with one or more groups selected from C 3-7 cycloalkyl, C 1-8 alkoxy, cyano, C 1-4 carboalkoxy, trifluoromethyl, C 1-8 alkylsulfonyl, halogen, nitro, hydroxy, trifluoromethoxy, C 1-8 carboxylate, amino, NR 13 R 14 , aryl and heteroaryl; and
(e) X is selected from S and O; with the proviso that when R 4 is isopropyl, then R 3 is not halogen.
[0036] In an alternative embodiment, the invention is directed to compounds of Formula I wherein R 1 , R 3 and R 4 are as described above and R 2 is —NR 15 R 16 wherein R 15 and R 16 are independently selected from hydrogen, optionally substituted C 1-8 straight or branched chain alkyl, arylalkyl, C 3-7 cycloalkyl, aryl, heteroaryl, and heterocyclyl or R 15 and R 16 taken together with the nitrogen form a heteroaryl or heterocyclyl group; with the proviso that when R 2 is NHR 16 , R 1 is not —COOR 6 where R 6 is ethyl.
[0037] This invention also provides a pharmaceutical composition comprising the instant compound and a pharmaceutically acceptable carrier.
[0038] This invention further provides a method of treating a subject having a condition ameliorated by antagonizing Adenosine A2a receptors or by reducing PDE activity in appropriate cells, which comprises administering to the subject a therapeutically effective dose of the instant pharmaceutical composition.
[0039] This invention further provides a method of preventing a disorder ameliorated by antagonizing Adenosine A2a receptors or by reducing PDE activity in appropriate cells in a subject, comprising administering to the subject a prophylactically effective dose of the compound of claim 1 either preceding or subsequent to an event anticipated to cause a disorder ameliorated by antagonizing Adenosine A2a receptors or reducing PDE activity in appropriate cells in the subject.
DETAILED DESCRIPTION OF THE INVENTION
[0040] Compounds of Formula 1 are potent small molecule antagonists of the Adenosine A2a receptors that have demonstrated potency for the antagonism of Adenosine A2a, A1, and A3 receptors.
[0041] Compounds of Formula I are also potent small molecule phosphodiesterase inhibitors that have demonstrated potency for inhibition of PDE7, PDE5, and PDE4. Some of the compounds of this invention are potent small molecule PDE7 inhibitors which have also demonstrated good selectivity against PDE5 and PDE4.
[0042] Preferred embodiments for R 1 are COOR 6 , wherein R 6 is selected from H, optionally substituted C 1-8 straight or branched chain alkyl, optionally substituted aryl and optionally substituted arylalkyl. Preferably R 6 is H, or C 1-8 straight or branched chain alkyl which may be optionally substituted with a substituent selected from CN and hydroxy.
[0043] Preferred embodiments for R 2 are optionally substituted heterocycle, optionally substituted aryl and optionally substituted heteroaryl. Preferred substituents are from one to three members selected from the group consisting of halogen, alkyl, alkoxy, alkoxyphenyl, halo, triflouromethyl, trifluoro or difluoromethoxy, amino, alkylamino, hydroxy, cyano, and nitro. Preferably, R 2 is optionally substituted furan, phenyl or napthyl or R 2 is
optionally substituted with from one to three members selected from the group consisting of halogen, alkyl, hydroxy, cyano, and nitro. In another embodiment of the instant compound, R 2 is —NR 15 R 16 .
[0044] Preferred substituants for R 3 include:
(i) hydrogen, halo, C 1-8 straight or branched chain alkyl, C 1-8 alkoxy, cyano, C 1-4 carboalkoxy, trifluoromethyl, C 1-8 alkylsulfonyl, halogen, nitro, and hydroxy; (ii) —NR 10 R 11 wherein R 10 and R 11 are independently selected from H, C 1-8 straight or branched chain alkyl, arylC 1-8 alkyl, C 3-7 cycloalkyl, carboxyC 1-8 alkyl, aryl, heteroaryl, and heterocyclyl or R 10 and R 11 taken together with the nitrogen form a heteroaryl or heterocyclyl group; (iii) —NR 12 COR 13 wherein R 12 is selected from hydrogen or alkyl and R 13 is selected from hydrogen, alkyl, substituted alkyl, C 1-3 alkoxyl, carboxyC 1-8 alkyl, aryl, arylalkyl, R 30 R 31 N(CH 2 ) p —, R 30 R 31 NCO(CH 2 ) p —, heteroaryl and heterocyclyl or R 12 and R 13 taken together with the carbonyl form a carbonyl containing heterocyclyl group, wherein, R 30 and R 31 are independently selected from H, OH, alkyl, and alkoxy, and p is an integer from 1-6.
[0048] Particularly, R 3 is selected from the group consisting of
[0049] Preferred embodiments for R 4 include hydrogen, C 1-3 straight or branched chain alkyl, particularly methyl, amine and amino.
[0050] In a further embodiment of the instant compound, R 1 is COOR 6 and R 2 is selected from the group consisting of substituted phenyl, and substituted naphthyl or R 2 is NR 15 R 16 .
[0051] More particularly, R 1 is COOR 6 where R 6 is alkyl, R 2 is substituted phenyl or naphthyl or R 2 is NR 15 R 16 , and R 3 is selected from the group consisting of H, nitro, amino, NHAc, halo, hydroxy, alkoxy, or a moiety of the formulae:
alkyl(CO)NH—, and R 4 is selected from hydrogen, C 1-3 straight or branched chain alkyl, particularly methyl, and amino.
[0052] In a preferred embodiment, the compound is selected from the group of compounds shown in Table 1 hereinafter.
[0053] More preferably, the compound is selected from the following compounds:
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 2-amino-4-(1,3-benzodioxol-5-yl)-5-oxo-, ethyl ester
[0054]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(6-bromo-1,3-benzodioxol-5-yl)-2-methyl-5-oxo-, ethyl ester
[0055]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 7-amino-4-(1,3-benzodioxol-5-yl)-2-methyl-5-oxo-, ethyl ester
[0056]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(6-bromo-1,3-benzodioxol-5-yl)-2-methyl-5-oxo-, methyl ester
[0057]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3,5-dimethylphenyl)-2-methyl-5-oxo-, methyl ester
[0058]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 8-(acetylamino)-4-(1,3-benzodioxol-5-yl)-2-methyl-5-oxo-, ethyl ester
[0059]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 2-methyl-4-(3-methylphenyl)-5-oxo-, methyl ester
[0060]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 7-amino-4-(3,5-dimethylphenyl)-2-methyl-5-oxo-, methyl ester
[0061]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 7-amino-2-methyl-4-(4-methyl-1-naphthalenyl)-5-oxo-, methyl ester
[0062]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3,5-dibromo-4-hydroxyphenyl)-2-methyl-8-nitro-5-oxo-, methyl ester
[0063]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 7,8-dichloro-4-(3,5-dibromo-4-hydroxyphenyl)-2-methyl-5-oxo-, methyl ester
[0064]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 7-bromo-4-(3,5-dibromo-4-hydroxyphenyl)-2-methyl-5-oxo-, methyl ester
[0065]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 8-bromo-4-(3,5-dibromo-4-hydroxyphenyl)-2-methyl-5-oxo-, methyl ester
[0066]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 8-[(3-carboxy-1-oxopropyl)amino]-4-(3,5-dimethylphenyl)-2-methyl-5-oxo-, methyl ester
[0067]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 8-[(3-carboxy-1-oxopropyl)amino]-2-methyl-4-(4-methyl-1-naphthalenyl)-5-oxo-, methyl ester
[0068]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3,5-dimethylphenyl)-8-[[4-(hydroxyamino)-1,4-dioxobutyl]amino]-2-methyl-5-oxo-, methyl ester
[0069]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3,5-dimethylphenyl)-8-[[[(2-hydroxyethyl)amino]acetyl]amino]-2-methyl-5-oxo-, methyl ester
[0070]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 8-[(4-carboxy-1-oxobutyl)amino]-4-(3,5-dimethylphenyl)-2-methyl-5-oxo-, methyl ester
[0071]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3,5-dimethylphenyl)-8-[[[(2-hydroxyethyl)methylamino]acetyl]amino]-2-methyl-5-oxo-, methyl ester
[0072]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3,5-dimethylphenyl)-2-methyl-8-[(4-morpholinylacetyl)amino]-5-oxo-, methyl ester
[0073]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3,5-dimethylphenyl)-2-methyl-5-oxo-8-[(1-piperazinylacetyl)amino]-, methyl ester
[0074]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-phenyl-2-amino-5-oxo-, ethyl ester
[0075]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(4-methylphenyl)-2-methyl-5-oxo-, methyl ester
[0076]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3-bromophenyl)-2-methyl-5-oxo-, methyl ester
[0077]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3-bromophenylamino)-2-methyl-5-oxo-, methyl ester
[0078]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-phenyl-2-amino-5-oxo-, methyl ester
[0079]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(2-furyl)-2-amino-5-oxo-, methyl ester
[0080]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(3-furyl)-2-amino-5-oxo-, methyl ester
[0081]
5H-indeno[1,2-b]pyridine-3-carboxylic acid, 4-(2-furyl)-2-amino-5-oxo-, ethyl ester
[0082] The instant compounds can be isolated and used as free bases. They can also be isolated and used as pharmaceutically acceptable salts. Examples of such salts include hydrobromic, hydroiodic, hydrochloric, perchloric, sulfuric, maleic, fumaric, malic, tartaric, citric, benzoic, mandelic, methanesulfonic, hydroethanesulfonic, benzenesulfonic, oxalic, palmoic, 2-naphthalenesulfonic, p-toluenesulfonic, cyclohexanesulfamic and saccharic.
[0083] This invention also provides a pharmaceutical composition comprising the instant compound and a pharmaceutically acceptable carrier.
[0084] Pharmaceutically acceptable carriers are well known to those skilled in the art and include, but are not limited to, from about 0.01 to about 0.1 M and preferably 0.05 M phosphate buffer or 0.8% saline. Such pharmaceutically acceptable carriers can be aqueous or non-aqueous solutions, suspensions and emulsions. Examples of non-aqueous solvents are propylene glycol, polyethylene glycol, vegetable oils such as olive oil, and injectable organic esters such as ethyl oleate. Aqueous carriers include water, ethanol, alcoholic/aqueous solutions, glycerol, emulsions or suspensions, including saline and buffered media. Oral carriers can be elixirs, syrups, capsules, tablets and the like. The typical solid carrier is an inert substance such as lactose, starch, glucose, methyl-cellulose, magnesium stearate, dicalcium phosphate, mannitol and the like. Parenteral carriers include sodium chloride solution, Ringer's dextrose, dextrose and sodium chloride, lactated Ringer's and fixed oils. Intravenous carriers include fluid and nutrient replenishers, electrolyte replenishers such as those based on Ringer's dextrose and the like. Preservatives and other additives can also be present, such as, for example, antimicrobials, antioxidants, chelating agents, inert gases and the like. All carriers can be mixed as needed with disintegrants, diluents, granulating agents, lubricants, binders and the like using conventional techniques known in the art.
[0085] This invention further provides a method of treating a subject having a condition ameliorated by antagonizing Adenosine A2a receptors or by reducing PDE activity in appropriate cells, which comprises administering to the subject a therapeutically effective dose of the instant pharmaceutical composition.
[0086] In one embodiment, the disorder is a neurodegenerative or movement disorder. In another embodiment, the disorder is an inflammatory disorder. In still another embodiment, the disorder is an AIDS-related disorder. Examples of disorders treatable by the instant pharmaceutical composition include, without limitation, Parkinson's Disease, Huntington's Disease, Multiple System Atrophy, Corticobasal Degeneration, Alzheimer's Disease, Senile Dementia, organ transplantation, autoimmune disorders (e.g. arthritis), immune challenge such as a bee sting, inflammatory bowel disease, bronchial disorders (e.g. asthma), HIV/AIDS, cardiovascular disorder, erectile dysfunction, allergies, and psoriasis.
[0087] In one preferred embodiment, the disorder is rheumatoid arthritis.
[0088] In another preferred embodiment, the disorder is Parkinson's disease.
[0089] As used herein, the term “subject” includes, without limitation, any animal or artificially modified animal having a disorder ameliorated by reducing PDE activity in appropriate cells. In a preferred embodiment, the subject is a human. In a more preferred embodiment, the subject is a human.
[0090] As used herein, “appropriate cells” include, by way of example, cells which display PDE activity. Specific examples of appropriate cells include, without limitation, T-lymphocytes, muscle cells, neuro cells, adipose tissue cells, monocytes, macrophages, fibroblasts.
[0091] Administering the instant pharmaceutical composition can be effected or performed using any of the various methods known to those skilled in the art. The instant compounds can be administered, for example, intravenously, intramuscularly, orally and subcutaneously. In the preferred embodiment, the instant pharmaceutical composition is administered orally. Additionally, administration can comprise giving the subject a plurality of dosages over a suitable period of time. Such administration regimens can be determined according to routine methods.
[0092] As used herein, a “therapeutically effective dose” of a pharmaceutical composition is an amount sufficient to stop, reverse or reduce the progression of a disorder. A “prophylactically effective dose” of a pharmaceutical composition is an amount sufficient to prevent a disorder, i.e., eliminate, ameliorate and/or delay the disorder's onset. Methods are known in the art for determining therapeutically and prophylactically effective doses for the instant pharmaceutical composition. The effective dose for administering the pharmaceutical composition to a human, for example, can be determined mathematically from the results of animal studies.
[0093] In one embodiment, the therapeutically and/or prophylactically effective dose is a dose sufficient to deliver from about 0.001 mg/kg of body weight to about 200 mg/kg of body weight of the instant pharmaceutical composition. In another embodiment, the therapeutically and/or prophylactically effective dose is a dose sufficient to deliver from about 0.05 mg/kg of body weight to about 50 mg/kg of body weight. More specifically, in one embodiment, oral doses range from about 0.05 mg/kg to about 100 mg/kg daily. In another embodiment, oral doses range from about 0.05 mg/kg to about 50 mg/kg daily, and in a further embodiment, from about 0.05 mg/kg to about 20 mg/kg daily in yet another embodiment, infusion doses range from about 1.0 μg/kg/min to about 10 mg/kg/min of inhibitor, admixed with a pharmaceutical carrier over a period ranging from about several minutes to about several days. In a further embodiment, for topical administration, the instant compound can be combined with a pharmaceutical carrier at a drug/carrier ratio of from about 0.001 to about 0.1.
[0094] This invention still further provides a method of preventing an inflammatory response in a subject, comprising administering to the subject a prophylactically effective amount of the instant pharmaceutical composition either preceding or subsequent to an event anticipated to cause the inflammatory response in the subject. In the preferred embodiment, the event is an insect sting or an animal bite.
DEFINITIONS AND NOMENCLATURE
[0095] Unless otherwise noted, under standard nomenclature used throughout this disclosure the terminal portion of the designated side chain is described first, followed by the adjacent functionality toward the point of attachment.
[0096] As used herein, the following chemical terms shall have the meanings as set forth in the following paragraphs: “independently”, when in reference to chemical substituents, shall mean that when more than one substituent exists, the substituents may be the same or different;.
[0097] “Alkyl” shall mean straight, cyclic and branched-chain alkyl. Unless otherwise stated, the alkyl group will contain 1-20 carbon atoms. Unless otherwise stated, the alkyl group may be optionally substituted with one or more groups such as halogen, OH, CN, mercapto, nitro, amino, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxyl, C 1 -C 8 -alkylthio, C 1 -C 8 -alkyl-amino, di(C 1 -C 8 -alkyl)amino, (mono-, di-, tri-, and per-) halo-alkyl, formyl, carboxy, alkoxycarbonyl, C 1 -C 8 -alkyl-CO—O—, C 1 -C 8 -alkyl-CO—NH—, carboxamide, hydroxamic acid, sulfonamide, sulfonyl, thiol, aryl, aryl(c 1 -c 8 )alkyl, heterocyclyl, and heteroaryl.
[0098] “Alkoxy” shall mean —O-alkyl and unless otherwise stated, it will have 1-8 carbon atoms.
[0099] The term “bioisostere” is defined as “groups or molecules which have chemical and physical properties producing broadly similar biological properties.” (Burger's Medicinal Chemistry and Drug Discovery, M. E. Wolff, ed. Fifth Edition, Vol. 1, 1995, Pg. 785).
[0100] “Halogen” shall mean fluorine, chlorine, bromine or iodine; “PH” or “Ph” shall mean phenyl; “Ac” shall mean acyl; “Bn” shall mean benzyl.
[0101] The term “acyl” as used herein, whether used alone or as part of a substituent group, means an organic radical having 2 to 6 carbon atoms (branched or straight chain) derived from an organic acid by removal of the hydroxyl group. The term “Ac” as used herein, whether used alone or as part of a substituent group, means acetyl.
[0102] “Aryl” or “Ar,” whether used alone or as part of a substituent group, is a carbocyclic aromatic radical including, but not limited to, phenyl, 1- or 2-naphthyl and the like. The carbocyclic aromatic radical may be substituted by independent replacement of 1 to 5 of the hydrogen atoms thereon with halogen, OH, CN, mercapto, nitro, amino, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxyl, C 1 -C 8 -alkylthio, C 1 -C 8 -alkyl-amino, di(C 1 -C 8 -alkyl)amino, (mono-, di-, tri-, and per-) halo-alkyl, formyl, carboxy, alkoxycarbonyl, C 1 -C 8 -alkyl-CO—O—, C 1 -C 8 -alkyl-CO—NH—, or carboxamide. Illustrative aryl radicals include, for example, phenyl, naphthyl, biphenyl, fluorophenyl, difluorophenyl, benzyl, benzoyloxyphenyl, carboethoxyphenyl, acetylphenyl, ethoxyphenyl, phenoxyphenyl, hydroxyphenyl, carboxyphenyl, trifluoromethylphenyl, methoxyethylphenyl, acetamidophenyl, tolyl, xylyl, dimethylcarbamylphenyl and the like. “Ph” or “PH” denotes phenyl.
[0103] Whether used alone or as part of a substituent group, “heteroaryl” refers to a cyclic, fully unsaturated radical having from five to ten ring atoms of which one ring atom is selected from S, O, and N; 0-2 ring atoms are additional heteroatoms independently selected from S, O, and N; and the remaining ring atoms are carbon. The radical may be joined to the rest of the molecule via any of the ring atoms. Exemplary heteroaryl groups include, for example, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyrroyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isoxazolyl, thiadiazolyl, triazolyl, triazinyl, oxadiazolyl, thienyl, furanyl, quinolinyl, isoquinolinyl, indolyl, isothiazolyl, 2-oxazepinyl, azepinyl, N-oxo-pyridyl, 1-dioxothienyl, benzothiazolyl, benzoxazolyl, benzothienyl, quinolinyl-N-oxide, benzimidazolyl, benzopyranyl, benzisothiazolyl, benzisoxazolyl, benzodiazinyl, benzofurazanyl, benzothiopyranyl, indazolyl, indolizinyl, benzofuryl, chromonyl, coumarinyl, cinnolinyl, quinoxalinyl, indazolyl, pyrrolopyridinyl, furopyridinyl (such as furo[2,3-c]pyridinyl, furo[3,2-b]pyridinyl, or furo[2,3-b]pyridinyl), imidazopyridinyl (such as imidazo[4,5-b]pyridinyl or imidazo[4,5-c]pyridinyl), naphthyridinyl, phthalazinyl, purinyl, pyridopyridyl, quinazolinyl, thienofuryl, thienopyridyl, thienothienyl, and furyl. The heteroaryl group may be substituted by independent replacement of 1 to 5 of the hydrogen atoms thereon with halogen, OH, CN, mercapto, nitro, amino, C 1 -C 8 -alkyl, C 1 -C 8 -alkoxyl, C 1 -C 8 -alkylthio, C 1 -C 8 -alkyl-amino, di(C 1 -C 8 -alkyl)amino, (mono-, di-, tri-, and per-) halo-alkyl, formyl, carboxy, alkoxycarbonyl, C 1 -C 8 -alkyl-CO—O—, C 1 -C 8 -alkyl-CO—NH—, or carboxamide. Heteroaryl may be substituted with a mono-oxo to give for example a 4-oxo-1H-quinoline.
[0104] The terms “heterocycle,” “heterocyclic,” and “heterocyclo” refer to an optionally substituted, fully or partially saturated cyclic group which is, for example, a 4- to 7-membered monocyclic, 7- to 11-membered bicyclic, or 10- to 15-membered tricyclic ring system, which has at least one heteroatom in at least one carbon atom containing ring. Each ring of the heterocyclic group containing a heteroatom may have 1, 2, or 3 heteroatoms selected from nitrogen atoms, oxygen atoms, and sulfur atoms, where the nitrogen and sulfur heteroatoms may also optionally be oxidized. The nitrogen atoms may optionally be quaternized. The heterocyclic group may be attached at any heteroatom or carbon atom.
[0105] Exemplary monocyclic heterocyclic groups include pyrrolidinyl; oxetanyl; pyrazolinyl; imidazolinyl; imidazolidinyl; oxazolyl; oxazolidinyl; isoxazolinyl; thiazolidinyl; isothiazolidinyl; tetrahydrofuryl; piperidinyl; piperazinyl; 2-oxopiperazinyl; 2-oxopiperidinyl; 2-oxopyrrolidinyl; 4-piperidonyl; tetrahydropyranyl; tetrahydrothiopyranyl; tetrahydrothiopyranyl sulfone; morpholinyl; thiomorpholinyl; thiomorpholinyl sulfoxide; thiomorpholinyl sulfone; 1,3-dioxolane; dioxanyl; thietanyl; thiiranyl; and the like. Exemplary bicyclic heterocyclic groups include quinuclidinyl; tetrahydroisoquinolinyl; dihydroisoindolyl; dihydroquinazolinyl (such as 3,4-dihydro-4-oxo-quinazolinyl); dihydrobenzofuryl; dihydrobenzothienyl; dihydrobenzothiopyranyl; dihydrobenzothiopyranyl sulfone; dihydrobenzopyranyl; indolinyl; isochromanyl; isoindolinyl; piperonyl; tetrahydroquinolinyl; and the like.
[0106] Substituted aryl, substituted heteroaryl, and substituted heterocycle may also be substituted with a second substituted-aryl, a second substituted-heteroaryl, or a second substituted-heterocycle to give, for example, a 4-pyrazol-1-yl-phenyl or 4-pyridin-2-yl-phenyl.
[0107] Designated numbers of carbon atoms (e.g., C 1-8 ) shall refer independently to the number of carbon atoms in an alkyl or cycloalkyl moiety or to the alkyl portion of a larger substituent in which alkyl appears as its prefix root.
[0108] Unless specified otherwise, it is intended that the definition of any substituent or variable at a particular location in a molecule be independent of its definitions elsewhere in that molecule. It is understood that substituents and substitution patterns on the compounds of this invention can be selected by one of ordinary skill in the art to provide compounds that are chemically stable and that can be readily synthesized by techniques known in the art as well as those methods set forth herein.
[0109] Where the compounds according to this invention have at least one stereogenic center, they may accordingly exist as enantiomers. Where the compounds possess two or more stereogenic centers, they may additionally exist as diastereomers. Furthermore, some of the crystalline forms for the compounds may exist as polymorphs and as such are intended to be included in the present invention. In addition, some of the compounds may form solvates with water (i.e., hydrates) or common organic solvents, and such solvates are also intended to be encompassed within the scope of this invention.
[0110] Some of the compounds of the present invention may have trans and cis isomers. In addition, where the processes for the preparation of the compounds according to the invention give rise to mixture of stereoisomers, these isomers may be separated by conventional techniques such as preparative chromatography. The compounds may be prepared as a single stereoisomer or in racemic form as a mixture of some possible stereoisomers. The non-racemic forms may be obtained by either synthesis or resolution. The compounds may, for example, be resolved into their components enantiomers by standard techniques, such as the formation of diastereomeric pairs by salt formation. The compounds may also be resolved by covalent linkage to a chiral auxiliary, followed by chromatographic separation and/or crystallographic separation, and removal of the chiral auxiliary. Alternatively, the compounds may be resolved using chiral chromatography.
[0111] This invention will be better understood by reference to the Experimental Details which follow, but those skilled in the art will readily appreciate that these are only illustrative of the invention as described more fully in the claims which follow thereafter. Additionally, throughout this application, various publications are cited. The disclosure of these publications is hereby incorporated by reference into this application to describe more fully the state of the art to which this invention pertains.
[0000] Experimental Details
[0000] I. General Synthetic Schemes
[0112] Representative compounds of the present invention can be synthesized in accordance with the general synthetic methods described below and illustrated in the following general schemes. The products of some schemes can be used as intermediates to produce more than one of the instant compounds. The choice of intermediates to be used to produce subsequent compounds of the present invention is a matter of discretion that is well within the capabilities of those skilled in the art.
[0113] Procedures described in Scheme 1, wherein R 3a , R 3b , R 3c , and R 3d are independently any R 3 group, and R 1 , R 2 , R 3 , and R 4 are as described above, can be used to prepare compounds of the invention wherein X is O.
[0114] Benzylidenes 2 may be obtained by known methods (Bullington, J. L; Cameron, J. C.; Davis, J. E.; Dodd, J. H.; Harris, C. A.; Henry, J. R.; Pellegrino-Gensey, J. L.; Rupert, K. C.; Siekierka, J. J. Bioorg. Med. Chem. Lett. 1998, 8, 2489; Petrow, V.; Saper, J.; Sturgeon, B. J. Chem. Soc. 1949, 2134). Hantzsch reaction of the benzylidene compounds with enamines 3 can be performed in refluxing acetic acid (Petrow et al., supra). When the desired enamines are not available, alternate Hantzsch conditions may be utilized which involve adding ammonium acetate to the reaction. The resulting dihydropyridines 4 are oxidized with chromium trioxide to obtain the desired pyridines 1 (Petrow et al., supra). In cases where the substitution pattern on the fused aromatic ring (R 3 ) leads to a mixture of regioisomers, the products can be separated by column chromatography.
[0115] In some cases, especially where R 2 is an alkyl group, another modification of the Hantzsch may be performed which uses three components (Bocker, R. H.; Buengerich, P. J. Med. Chem. 1986, 29,1596). Where R 2 is an alkyl group it is also necessary to perform the oxidation with DDQ or MnO 2 instead of chromium (VI) oxide (Vanden Eynde, J. J.; Delfosse, F.; Mayence, A.; Van Haverbeke, Y. Tetrahedron 1995, 51, 6511).
[0116] In order to obtain the corresponding carboxylic acids and amides, the cyanoethyl esters 5 are prepared as described above. The esters are converted to the carboxylic acids by treatment with sodium hydroxide in acetone and water (Ogawa, T.; Matsumoto, K.; Yokoo, C.; Hatayama, K.; Kitamura, K. J. Chem. Soc., Perkin Trans. 1 1993, 525). The corresponding amides can then be obtained from the acids using standard means.
[0117] The procedure for making compounds where R 4 is NH 2 may be slightly modified. These compounds are prepared in one step from the benzylidenes 2 and alkyl amidinoacetate (Kobayashi, T.; Inoue, T.; Kita, Z.; Yoshiya, H.; Nishino, S.; Oizumi, K.; Kimura, T. Chem. Pharm. Bull. 1995, 43, 788) as depicted in Scheme 4 wherein R is R 5 or R 6 as described above.
[0118] The dihydropyridine lactones 9 can be synthesized from benzylidenes 8 (Zimmer, H.; Hillstrom, W. W.; Schmidt, J. C.; Seemuth, P. D.; Vogeli, R. J. Org. Chem. 1978, 43, 1541) and 1,3-indanedione, as shown in Scheme 5, and the corresponding pyridine is then obtained by oxidation with manganese dioxide.
[0119] Representative schemes to modify substituents on the fused aromatic ring are shown below. The amines 11 are obtained from the corresponding nitro compounds 10 by reduction with tin (II) chloride (Scheme 6). Reaction of the amines with acetyl chloride provide the amides 12.
[0120] In accordance with Scheme 7 wherein Y is O, and n is an integer from 1-3, an alkyl chain with a carboxylic acid at the terminal end can also be added to the amines 11. For example, reaction with either succinic anhydride (Omuaru, V. O. T.; Indian J. Chem., Sect B. 1998, 37, 814) or β-propiolactone (Bradley, G.; Clark, J.; Kernick, W. J. Chem. Soc., Perkin Trans. 1 1972, 2019) can provide the corresponding carboxylic acids 13. These carboxylic acids are then converted to the hydroxamic acids 14 by treatment with ethyl chloroformate and hydroxylamine (Reddy, A. S.; Kumar, M. S.; Reddy, G. R. Tetrahedron Lett. 2000, 41, 6285).
[0121] The amines 11 can also be treated with glycolic acid to afford alcohols 15 (Jursic, B. S.; Zdravkovski, Z. Synthetic Comm. 1993, 23, 2761) as shown in Scheme 8.
[0122] As shown in Scheme 9, the aminoindenopyridines 11 may also be treated with chloroacetylchloride followed by amines to provide the more elaborate amines 16 (Weissman, S. A.; Lewis, S.; Askin, D.; Volante, R. P.; Reider, P. J. Tetrahedron Lett. 1998, 39, 7459). Where R 6 is a hydroxyethyl group, the compounds can be further converted to piperazinones 17.
[0123] The 4-aminoindenopyridines 19 can be synthesized from the 4-chloroindenopyridines 18 using a known procedure (Gorlitzer, K.; Herbig, S.; Walter, R. D. Pharmazie 1997, 504) or via palladium catalyzed coupling (Scheme 10).
[0124] Cyanoesters 20 can be prepared by known methods (Lee, J.; Gauthier, D.; Rivero, R. A. J. Org. Chem. 1999, 64, 3060). Reaction of 20 with enaminone 21 (Iida, H.; Yuasa, Y.; Kibayashi, C. J. Org. Chem. 1979, 44, 1074) in refluxing 1-propanol and triethylamine gave dihydropyridine 22, wherein R is R 5 or R 6 as described above, (Youssif, S.; EI-Bahaie, S.; Nabih, E. J. Chem. Res. ( S ) 1999, 112 and Bhuyan, P.; Borush, R. C.; Sandhu, J. S. J. Org. Chem. 1990, 55, 568), which can then be oxidized and subsequently deprotected to give pyridine 23.
II. Specific Compound Syntheses
[0125] Specific compounds which are representative of this invention can be prepared as per the following examples. No attempt has been made to optimize the yields obtained in these reactions. Based on the following, however, one skilled in the art would know how to increase yields through routine variations in reaction times, temperatures, solvents and/or reagents.
[0126] The products of certain syntheses can be used as intermediates to produce more than one of the instant compounds. In those cases, the choice of intermediates to be used to produce compounds of the present invention is a matter of discretion that is well within the capabilities of those skilled in the art.
EXAMPLE 1
Hantzsch Condensation to Form Dihydropyridine 4
(R 1 ═COOMe; R 2 =3,5-dimethylphenyl; R 3b,c ═Cl: R 3a,b ═H: R 4 =Me)
[0127] To a refluxing solution of benzylidene 2 (0.500 g, 1.5 mmol) in acetic acid (10 mL) was added methyl-3-aminocrotonate (0.695 g, 6.0 mmol). The reaction was heated to reflux for 20 minutes, then water was added until a precipitate started to form. The reaction was cooled to room temperature. The mixture was filtered and washed with water to obtain 0.354 g (55%) of a red solid. MS m/z 450 (M + +23), 428 (M + +1).
EXAMPLE 2
Alternate Hantzsch Conditions to Form Dihydropyridine 4
(R 1 ═CO 2 Me; R 2 =2,4-dimethylphenyl; R 3 ═H; R 4 =Et)
[0128] To a refluxing solution of benzylidene 2 (1.00 g, 3.82 mmol) in acetic acid (12 MI) was added methyl propionylacetate (1.98 g, 15.2 mmol) and ammonium acetate (1.17 g, 15.2 mmol). The reaction was heated for 20 min and then cooled to room temperature. No product precipitated from the solution, so the reaction was heated to reflux and then water was added until a solid began to precipitate. After cooling to room temperature, the mixture was filtered and the red solid washed with water to yield 1.29 g (90%) of product. MS m/z 396 (M + +23), 374 (M + +1).
EXAMPLE 3
Oxidation of Dihydropyridine 4 to Pyridine 1
(R 1 ═COOMe; R 2 =3,5-dimethylphenyl; R 3b,c ═Cl; R 3a,d ═H; R 4 =Me)
[0129] To a refluxing solution of dihydropyridine 4 (0.250 g, 0.58 mmol) in acetic acid (10 mL) was added a solution of chromium (VI) oxide (0.584 g, 0.58 mmol) in 1 mL water. After 30 minutes at reflux, the reaction was diluted with water until a precipitate started to form. The mixture was cooled to room temperature and allowed to stand overnight. The mixture was filtered and washed with water to give 0.199 g (81%) of a yellow solid. MS m/z 448 (M + +23), 426 (M + +1).
EXAMPLE 4
Oxidation of Dihydropyridine 4 to Pyridine 1
(R 1 ═COOMe; R 2 =(4-methyl)-1-naphthyl; R 3b,c ═H, NO 2 /NO 2 , H; R=Me)
[0130] To a refluxing suspension of regioisomeric dihydropyridines 4 (3.59 g, 8.16 mmol) in acetic acid (40 mL) was added a solution of chromium (VI) oxide (0.816 g, 8.16 mmol) in 3 mL water. After 20 minutes at reflux, the reaction was diluted with water until a precipitate started to form. The mixture was cooled to room temperature and allowed to stand overnight. The mixture was filtered and washed with water to yield the mixture of regioisomers as a yellow solid. The products were purified by column chromatography eluting with hexanes:ethyl acetate to yield 1.303 g (37%) of pyridine 1 (R 3b ═NO 2 ; R 3c ═H) and 0.765 g (21%) of its regioisomer (R 3b ═H: R 3c ═NO 2 ). MS m/z 461 (M + +23), 439 (M + +1).
EXAMPLE 5
Alternate Three Component Hantzsch Reaction to Form Dihydropyridine 4
(R 1 ═CO 2 Me; R 2 =cyclohexyl; R 3 ═H; R 4 =Me)
[0131] Cyclohexane carboxaldehyde (2.0 g, 17.8 mmol), 1,3-indandione (2.6 g, 17.8 mmol), methylacetoacetate (2.0 g, 17.8 mmol), and ammonium hydroxide (1 mL) were refluxed in 8 mL of methanol for 1.5 hours. The temperature was lowered to approximately 50° C. and the reaction was stirred overnight. The reaction was cooled to room temperature, filtered and the solid washed with water. The residue was then dissolved in hot ethanol and filtered while hot. The filtrate was concentrated to yield 4.1 g (68%) of the product which was used without purification. MS m/z 336 (M − −1).
EXAMPLE 6
DDQ Oxidation of Dihydropyridine 4
(R 1 ═CO 2 Me; R 2 =cyclohexyl; R 3 ═H: R 4 =Me)
[0132] To a solution of dihydropyridine 4 (2.50 g, 7.40 mmol) in 15 mL of dichloromethane was added 2,3-dichloro-3,6-dicyano-1,4-benzoquinone (1.70 g, 7.40 mmol). The reaction was stirred at room temperature for four hours. The mixture was filtered and the residue was washed with dichloromethane. After the filtrate was concentrated, the residue was purified by column chromatography eluting with ethyl acetate: hexanes to yield 0.565 g (23%) of a yellow solid. MS m/z 358 (M + +23), 336 (M + +1).
EXAMPLE 7
MnO 2 Oxidation of Dihydropyridine 4
(R 1 ═CO 2 Me; R 2 =4-(dimethylamino)phenyl; R 3 ═H; R 4 =Me)
[0133] To a solution of dihydropyridine 4 (0.50 g, 1.3 mmol) in 10 mL of dichloromethane was added manganese dioxide (2.5 g, 28.7 mmol). The reaction was stirred at room temperature overnight before filtering and washing with dichloromethane. The filtrate was concentrated to yield 0.43 g (88%) of orange solid 1. MS m/z 395 (M + +23), 373 (M + +1).
EXAMPLE 8
Cleavage of Carboxylic Ester 5
(R 2 =2,4-dimethylphenyl; R 3 ═H; R 4 =Me)
[0134] To a suspension of ester 5 (2.75 g, 6.94 mmol) in acetone (50 mL) was added aqueous 1 M NaOH (100 mL). After stirring at room temperature for 24 hours, the reaction mixture was diluted with 100 mL of water and washed with dichloromethane (2×100 mL). The aqueous layer was cooled to 0° C. and acidified with concentrated HCl. The mixture was filtered and washed with water to yield 1.84 g (77%) yellow solid 6. MS m/z 366 (M + +23), 343 (M + +1).
EXAMPLE 9
Preparation of Amide 7
(R 2 =2,4-dimethylphenyl; R 3 ═H; R 4 =Me; R 5 ═H: R 6 =Me)
[0135] A solution of carboxylic acid 6 (0.337 g, 0.98 mmol) in thionyl chloride (10 mL) was heated at reflux for 1 hour. The solution was cooled and concentrated in vacuo. The residue was diluted with CCl 4 and concentrated to remove the residual thionyl chloride. The residue was then dissolved in THF (3.5 mL) and added to a 0° C. solution of methylamine (1.47 mL of 2.0 M solution in THF, 2.94 mmol) in 6.5 mL THF. The reaction was warmed to room temperature and stirred overnight. The mixture was poured into water, filtered, washed with water and dried to yield 0.263 g (75%) of tan solid. MS m/z 357 (M + +1).
EXAMPLE10
Preparation of Pyridine 1
(R 1 ═CO 2 Et; R 2 =4-nitrophenyl; R 3 ═H; R 4 ═NH 2 )
[0136] To a refluxing solution of benzylidene 2 (1.05 g, 3.76 mmol) in 10 mL of acetic acid was added ethyl amidinoacetate acetic acid salt (0.720 g, 3.76 mmol). The resulting solution was heated at reflux overnight. After cooling to room temperature, the resulting precipitate was removed by filtration and washed with water. This impure residue was heated in a minimal amount of ethanol and then filtered to yield 0.527 g (35%) of a yellow solid. MS m/z 412 (M + +23), 390 (M + +1).
EXAMPLE 11
Hantzsch Condensation of Benzylidene 8
(R 2 =3-methoxyphenyl) and 1,3-indandione)
[0137] The benzylidene 8 (2.00 g, 9.2 mmol), 1,3-indandione (1.34 g, 0.2 mmmol) and ammonium acetate (2.83 g, 36.7 mmol) were added to 30 mL of ethanol and heated to reflux overnight. The reaction mixture was cooled to room temperature and diluted with ethanol. A yellow precipitate was collected by filtration, washed with ethanol, and dried under vacuum to yield 1.98 g (63%) of the dihydropyridine 9. MS m/z 346 (M + +1).
EXAMPLE 12
Reduction to Prepare Amine 11
(R 1 ═CO 2 Me; R 2 =4-methylnaphthyl; R 4 =Me)
[0138] To a refluxing suspension of pyridine 10 (0.862 g, 1.97 mmol) in 35 mL of ethanol was added a solution of tin (II) chloride dihydrate (1.33 g, 5.90 mmol) in 6 mL of 1:1 ethanol: concentrated HCl. The resulting solution was heated at reflux overnight. Water was added until a precipitate started to form and the reaction was cooled to room temperature. The mixture was then filtered and washed with water. After drying, the residue was purified by column chromatography eluting with hexanes: ethyl acetate to yield 0.551 g (69%) of an orange solid. MS m/z 431 (M + +23), 409 (M + +1).
EXAMPLE 13
Acetylation of Amine 11
(R 1 ═CO 2 Et; R 2 =3,4-methylenedioxyphenyl; R 4 =Me)
[0139] To a solution of amine 11 (0.070 g, 0.174 mmol) in 15 mL of dichloromethane was added triethylamine (0.026 g, 0.261 mmol) and acetyl chloride (0.015 g, 0.192 mmol). After stirring overnight at room temperature, the reaction mixture was diluted with water and then extracted with dichloromethane (3×35 mL). The combined organics were washed with brine, dried over MgSO 4 , and concentrated. The residue was purified by silica gel chromatography eluting with hexanes: ethyl acetate to yield 0.054 g (70%) of amide 12. MS m/z 467 (M + +23), 445 (M + +1).
EXAMPLE 14
Preparation of Carboxylic Acid 13
(R 1 ═CO 2 Me: R 2 =3,5-dimethylphenyl; R 4 =Me; Y═O; n=2)
[0140] To a suspension of amine 11 (0.079 g, 0.212 mmol) in 5 mL of benzene was added succinic anhydride (0.021 g, 0.212 mmol). After heating at reflux for 24 hours, the reaction mixture was filtered and washed with benzene. The residue was dried under high vacuum and then washed with ether to remove the excess succinic anhydride. This yielded 0.063 g (63%) of carboxylic acid 13. MS m/z 473 (M + +1).
EXAMPLE 15
Preparation of Carboxylic Acid 13
(R 1 ═CO 2 Me: R 2 =3,5-dimethylphenyl; R 4 =Me; Y═H 2 : n=1)
[0141] To a refluxing solution of amine 11 (0.078 g, 0.210 mmol) in 5 mL of acetonitrile was added β-propiolactone (0.015 g, 0.210 mmol). The reaction was heated to reflux for 72 hours before cooling to room temperature. The reaction mixture was concentrated. The residue was mixed with 10% aqueous sodium hydroxide and washed sequentially with ether and ethyl acetate. The aqueous layer was acidified with concentrated HCl and extracted with dichloromethane (2×25 mL). The combined organics were dried over MgSO 4 , filtered, and concentrated. The residue was purified by column chromatography eluting with 5% MeOH in dichloromethane to yield 0.020 g (21%) of an orange solid. MS m/z 467 (M + +23), 445 (M + +1).
EXAMPLE 16
Preparation of Hydroxamic Acid 14
(R 1 ═CO 2 Me; R 2 =(4-methyl)-1-naphthyl; Y═O; n=2; R 4 =Me)
[0142] To a 0° C. suspension of carboxylic acid 13 (.0.054 g, 0.106 mmol) in 10 mL of diethyl ether was added triethylamine (0.014 g, 0.138 mmol) and then ethyl chloroformate (0.014 g, 0.127 mmol). The mixture was stirred at 0° C. for 30 minutes and them warmed to room temperature. A solution of hydroxylamine (0.159 mmol) in methanol was added and the reaction was stirred overnight at room temperature. The mixture was filtered and the residue was washed with ether and dried under vacuum to yield 0.030 g (54%) of a yellow solid. MS m/z 524 (M + +1).
EXAMPLE 17
Preparation of Amide 15
(R 1 ═CO 2 Me; R 2 =3,5-dimethylphenyl; R 4 =Me)
[0143] A mixture of amine 11 (0.201 g, 0.54 mmol) and glycolic acid (0.049 g, 0.65 mmol) was heated at 120-160° C. for 30 minutes. During heating, more glycolic acid was added to ensure that excess reagent was present. Once the starting material was consumed, the reaction was cooled to room temperature, and diluted with dichloromethane. The resulting mixture was extracted with 20% NaOH, followed by 10% HCl, and finally water. The combined organics were concentrated and triturated with ether. Purification by column chromatography eluting with ethyl acetate:hexanes yielded 0.012 g (5%) of a yellow solid. MS m/z 453 (M + +23), 431 (M + +1).
EXAMPLE 18
Preparation of Amide 16
(R 1 ═CO 2 Me; R 2 =3,5-dimethylphenyl; R 4 =Me: NR 6 R 7 =morpholino)
[0144] To a 0° C. mixture of amine 11 (0.123 g, 0.331 mmol) in 2 mL of 20% aqenius NaHCO 3 and 3 mL of ethyl acetate was added chloroacetyl chloride (0.047 g, 0.413 mmol). The reaction was warmed to room temperature and stirred for 45 minutes. The mixture was poured into a separatory funnel and the aqueous layer was removed. The organic layer containing the crude chloroamide was used without purification. To the ethyl acetate solution was added morpholine (0.086 g, 0.992 mmol) and the reaction was heated to approx. 65° C. overnight. The reaction was diluted with water and cooled to room temperature. After extraction with ethyl acetate (3×25 mL), the combined organics were washed with brine, dried over MgSO 4 and concentrated to yield 0.130 g (79%) of a yellow solid. MS m/z 522 (M + +23), 500 (M + +1).
EXAMPLE 19
Preparation of Piperazinone 17
(R 1 ═CO 2 Me: R 2 =3,5-dimethylphenyl; R 4 =Me; R 7 ═H)
[0145] To a 0° C. solution of amide 16 (R 6 ═CH 2 CH 2 OH) (0.093 g, 0.20 mmol), tri n-butylphosphine (0.055 g, 0.27 mmol) in 0.35 mL ethyl acetate was slowly added di-tert-butyl azodicarboxylate (0.062 g, 0.27 mmol) in 0.20 mL ethyl acetate. The reaction was allowed to stand for 15 minutes and then heated to 40° C. overnight. 4.2 M ethanolic HCl was added dropwise. The mixture was cooled to 0° C. and allowed to stand for 2 hours. The mixture was filtered and washed with cold ethyl acetate. Purification by column chromatography with 1-5% MeOH in CH 2 Cl 2 yielded 0.011 (12%) of a white solid. MS m/z 478 (M + +23), 456 (M + +1).
EXAMPLE 20
Preparation of 4-Aminoindenopyridine 19
(R 1 ═CO 2 Me; R 4 =Me; R 6 =Me; R 7 =phenyl)
[0146] To a solution of 4-chloroindenopyridine 18 (0.069 g, 0.240 mmol) in 10 mL of 2-ethoxyethanol was added N-methylaniline (0.026 g, 0.240 mmol). The reaction was heated at reflux for 96 hours. After cooling to room temperature, the solution was concentrated. The residue was purified by column chromatography eluting with hexanes: ethyl acetate to yield 0.029 g (34%) of an orange solid. MS m/z 359 (M + +1).
EXAMPLE 21
Preparation of 4-Aminoindenopyridine 19
(R 1 ═CO 2 Me: R 4 =Me; R 6 ═H: R 7 =cyclopentyl) by Palladium Catalyzed Coupling
[0147] A mixture of 4-chloroindenopyridine 18 (0.100 g, 0.347 mmol), cyclopentylamine (0.035 g, 0.416 mmol), palladium (II) acetate (0.004 g, 0.0017 mmol), 2-(di-t-butylphosphino)biphenyl (0.010 g, 0.0035 mmol), and cesium carbonate (0.124 g, 0.382 mmol) in 10 mL of dioxane was heated at reflux overnight. The reaction was cooled to room temperature, diluted with water, and extracted with ethyl acetate (3'35 mL). The combined organics were washed with brine, dried over Na 2 SO 4 , and concentrated. The residue was purified by column chromatography eluting with ethyl acetate:hexanes. The purified oil was dissolved in ether and cooled to 0° C. To this solution was slowly added 1.0 M HCl in ether. The resulting precipitate was isolated by filtration, washed with ether, and dried under vacuum to yield 0.032 g (25%) of a yellow solid. MS m/z 359 (M + +23), 337 (M + +1).
EXAMPLE 22
Preparation of Dihydropyridine 21 (R 1 ═CO 2 Me: R 2 =2-furyl; R 3 ═H; R 4 ═NH 2 )
[0148] Unsaturated cyanoester 20 (0.20 g, 1.10 mmol), enamine 21 (0.20 g, 0.75 mmol) and 5 drops of triethylamine were refluxed in 1-propanol (4 mL). After 3 hours, the reaction was concentrated to half the volume and cooled. The resulting precipitate was filtered and washed with 1-propanol. The precipitate was a mixture of products and therefore was combined with the filtrate and concentrated. Purification by column chromatography, eluting with ethyl acetate: hexane yielded 0.11 g (34%) of the red product 22. MS m/z 465 (M + +23).
EXAMPLE 23
DDQ Oxidation/Deprotection of Dihydropyridine 22
(R 1 ═CO 2 Me; R 2 =3-furyl; R 3 ═H; R 4 ═NH 2 )
[0149] To a solution of dihydropyridine 22(0.05 g, 0.11 mmol) in chlorobenzene (4 mL) was added 2,3-dichloro-3,6-dicyano-1,4-benzoquinone (0.05 g, 0.22 mmol). The reaction was refluxed overnight before cooling to room temperature and diluting with diethyl ether. The reaction mixture was filtered through celite and concentrated in vacuo. Purification by column chromatography, eluting with ethyl acetate:hexane yielded 0.018 g (52%) of yellow product 23. MS m/z 343 (M + +23), 321 (M + +1).
[0150] Following the general synthetic procedures outlined above and in Examples 1-21, the compounds of Table 1 below were prepared.
TABLE 1 Ia MS No. R 1 R 2 R 3a R 3b R 3c R 3d R 4 (M + 1) 1 CN H H H H Me 341 2 CO 2 Et H H H H Me 388 3 CO 2 t-Bu H H H H Me 416 4 CO 2 t-Bu H H H H Me 432 5 CO 2 Et H H H H Me 389 6 CO 2 H H H H H Me 360 7 CO 2 Et H H H H Me 480 8 CO 2 Et H H H H Me 482 9 CO 2 Et H H H H Me 424 10 CO 2 H H H H H Me 376 11 CO 2 Et Ph H H H H Me 344 12 CO 2 Et H H H H Me 374 13 CO 2 Et H H H H Me 434 14 CO 2 Et H H H H Me 454 15 CO 2 Bn H H H H Me 450 169 H H H H Me 507 17 CO 2 Me H H H H Me 390 18 CO 2 Me H H H H Me 374 19 CO 2 Et H H H H Me 404 20 CO 2 Et H H H H Me 404 21 CO 2 Et H H H H Me 454 22 CO 2 Et H H H H NH 2 411 (M + 23) 23 CO 2 Et H H H H Me 388 25 CO 2 Et H H H H NH 2 405 26 CO 2 Et H H H H NH 2 390 27 CO 2 Et Ph H H H H NH 2 345 28 CO 2 Et H H H H Me 402 29 CO 2 Et H H H H Me 483 30 CO 2 Me Ph H H H H Me 330 31 CO 2 Et H H H H Me 402 32 CO 2 Et H NO 2 H H Me 433 33 H H H H Me 413 34 CO 2 Et H H H H Me 433 35 CO 2 Et H H NO 2 H Me 433 36 CO 2 Me H H H H Me 398 37 CO 2 Et H H NH 2 H Me 403 38 CONH 2 H H H H Me 359 39 CO 2 Et H H H H Me 372 40 CO 2 Et H NH 2 H H Me 403 41 CO 2 Et H H H H Me 334 42 CO 2 Et 2-Thienyl H H H H Me 350 43 CO 2 Me H H H H Me 358 44 CO 2 Me H H H H Me 388 45 CO 2 Me H H H H Me 419 46 CO 2 Me H H H H Me 388 47 CO 2 Me 4-Pyridyl H H H H Me 331 48 CO 2 Me H H H H Me 374 49 CO 2 Me H H H H Me 454 50 CO 2 Me H H H H Me 439 51 CO 2 Me H H H H Me 358 52 CO 2 Et H H H H Me 372 53 CO 2 Me H H H H Me 410 54 CO 2 Me H H H H Me 375 55 CO 2 Et H NHAc H H Me 445 56 CO 2 Et H H NHAc H Me 445 57 CO 2 Et H H H H Me 358 58 CO 2 Et H H H H Me 358 59 CO 2 Et H H H H Me 358 60 CO 2 Et H NO 2 H H Me 457 61 CO 2 Et H H NO 2 H Me 457 62 CO 2 Me H H H H Me 344 63 CO 2 Et H NH 2 H H Me 427 64 CO 2 Et H H NH 2 H Me 427 65 CO 2 Me H H H H Me 466 66 CO 2 Me H H H H Me 344 67 CO 2 Me H H H H Me 344 68 CO 2 Me H NO 2 H H Me 443 69 CO 2 Me H H NO 2 H Me 443 70 CO 2 Et H H H H i-Pr 400 71 CO 2 Me H NH 2 H H Me 413 72 CO 2 Me H H H H Me 399 73 CO 2 Me H H H H Et 372 74 CO 2 Me H H H H Me 398 75 CO 2 Me H H H H Me 394 76 CO 2 Me H H H H Me 372 77 CO 2 Me H NO 2 H H Me 403 78 CO 2 Me H H NO 2 H Me 403 79 CO 2 Me H H H H Me 394 80 CO 2 Me H NHAc H H Me 455 81 CO 2 Me H H H H Me 488 82 CO 2 Me H NH 2 H H Me 373 83 CO 2 Me H H NH 2 H Me 373 84 CO 2 Me H H H H Me 362 85 CO 2 Me H H H H Me 431 (M + 23) 86 CO 2 Me H H H H Me 380 (M + 23) 87 CO 2 Me H NO 2 H H Me 439 88 CO 2 Me H H NO 2 H Me 439 89 CO 2 Me H H H H Me 430 90 CO 2 Me H NH 2 H H Me 409 91 CO 2 Me H H NH 2 H Me 409 92 H H H H Me 397 93 CN H H H H Me 325 94 CO 2 Me H H H H NH 2 359 95 CO 2 Me H H H H NH 2 395 96 CO 2 H H H H H Me 344 97 H H H H Me 433 98 CN H H H H Me 361 99 H H H H C 2 H 2 O 2 358 100 H H H H C 2 H 2 O 2 357 101 Ph H H H H C 2 H 2 O 2 314 102 p-C 6 H 4 NO 2 H H H H C 2 H 2 O 2 361 103 H H H H C 2 H 2 O 2 364 104 H H H H C 2 H 2 O 2 342 105 CO 2 H H H H H Me 380 106 CONH 2 H H H H Me 343 107 CONHMe H H H H Me 357 108 CONMe 2 H H H H Me 371 109 H H H H C 2 H 2 O 2 378 110 H H H H C 2 H 2 O 2 328 111 H H H H C 2 H 2 O 2 356 112 H H H H C 2 H 2 O 2 328 113 CO 2 Me H H H H Me 375 114 H H H H C 2 H 2 O 2 328 115 CO 2 Me H H H H Me 373 116 CONH 2 H H H H Me 379 117 H H H H C 2 H 2 O 2 365 118 CO 2 Me H H H H Me 375 119 CONHMe H H H H Me 393 120 CONMe2 H H H H Me 407 121 CO 2 Me H H H H Me 381 122 CO 2 Me H Cl Cl H Me 463 123 CO 2 Me H Cl Cl H Me 427 124 CO 2 Me H H H H Me 381 125 CO 2 Et H H H H Me 408 126 CO 2 Me H Cl Cl H Me 555 127 CO 2 Me Cl H H Cl Me 427 128 CO 2 Me 2-NO 2 -4,5-OCH 2 O—C 6 H 2 H H H H Me 421 129 CO 2 Me Cl H H Cl Me 558 130 CO 2 Me H H H H Me 345 131 CO 2 Et H Cl Cl H Me 477 132 CO 2 Me H H H H Me 503 133 Ac H H H H Me 472 134 Ac H H H H Me 342 135 CO 2 Me H H H H Me 331 136 H H H H Me 527 137 H H H H Me 397 138 CO 2 Me H H H H Me 362 139 CO 2 H H H H H Me 474 140 CO 2 H H H H H Me 344 141 CO 2 Me H H H H Me 346 142 CO 2 Me H H H H Me 380 143 CO 2 Me H H H H Me 486 144 CO 2 Me H H H H Me 436 145 CO 2 Me H H H H Me 518 146 H H H H Me 557 147 H Cl Cl H Me 466 148 CO 2 Et —NHPh H H H H Me 359 149 CO 2 Me H H H H Me 360 150 CO 2 Me H H H H Me 504 151 H H H H Me 420 152 C 3 H 5 O 3 H H H H Me 534 153 H H H H Me 385 154 H H H H Me 373 155 H H NO 2 H Me 574 156 CO 2 Me H Br H H Me 473 157 CO 2 Me H H Br H Me 473 158 H Cl Cl H Me 489 159 H H NO 2 H Me 590 160 H H H H Me 411 161 CO 2 Me H Br H H Me 436 162 CO 2 Me H H Br H Me 438 163 CO 2 Me H Br Br H Me 516 164 H Cl Cl H Me 597 165 H Cl Cl H Me 480 166 CO 2 Me H Br Br H Me 552 167 CO 2 Et H Br Br H Me 530 168 CO 2 Me F H H F Me 540 169 CO 2 Me H H NO 2 H Me 551 170 CO 2 Me H Cl Cl H Me 573 171 H H NO 2 H Me 444 172 H NO 2 H H Me 444 173 CO 2 Me F H H F Me 394 174 F H H F Me 433 175 CO 2 Me H Br Br H Me 548 176 CO 2 Me H H H H Me 355 177 CO 2 Me H NO 2 H H Me 421 178 CO 2 Me H H NO 2 H Me 453 (M + 23) 179 CO 2 Me H Cl Cl H Me 443 180 CN H H H H Me 341 181 CO 2 Me H H H H Me 598 182 CO 2 Me H Cl Cl H Me 435 183 CO 2 Et H H H H Me 387 184 CO 2 Et H H H H Me 373 185 CO 2 Me H H H H Me 612 186 CO 2 Et H H H H Me 410 187 CO 2 Me H H NO 2 H Me 345 188 CO 2 Me H Cl Cl H Me 668 189 CO 2 Me H H NO 2 H Me 413 190 CO 2 H H Cl Cl H Me 544 191 CN H H H H Me 565 192 CO 2 Me H Br H H Me 606 (M + 23) 193 CO 2 Me H H Br H Me 584 194 CO 2 Et H H H H Me 373 195 CO 2 Et H H H H Me 427 196 CO 2 Et H Cl Cl H Me 587 197 CO 2 Et H H H H Me 437 198 CO 2 Et H H H H Me 389 199 CO 2 Et H H H H Me 612 200 CO 2 Et H Cl Cl H Me 449 201 CO 2 Me H Cl Cl H Me 450 202 CO 2 Me H Cl Cl H Me 465 203 CO 2 Me H H H H Me 396 204 CO 2 Me H H H Me 473 205 CO 2 Me H H H H Me 345 206 CO 2 Me H H H H Me 359 207 CO 2 Me H Cl Cl H Me 444 208 CO 2 Me H H H H Me 355 209 CO 2 H H H H H Me 366 210 CO 2 Me H Cl Cl H Me 444 211 CO 2 Me H Cl Cl H Me 430 212 CO 2 Me H H H H Me 416 213 CO 2 Me H Cl Cl H Me 430 214 CO 2 Me H H H H Me 413 215 CO 2 Me H OMe OMe H Me 418 216 CO 2 Me H OMe OMe H Me 454 217 CO 2 Me H H H H Me 362 218 CO 2 Me H H H Me 445 219 CO 2 Me H H H H Me 359 220 CO 2 Me —NHPh H H H H Me 345 221 CO 2 Me H H H H Me 423 222 CO 2 Me 2-Pyridyl H H H H Me 353 (M + 23) 223 CO 2 Me H OMe OMe H Me 459 224 CO 2 Me H Cl Cl H Me 485 225 CO 2 Me H H H H Me 345 226 CO 2 Me H H NO 2 H Me 420 227 CO 2 Me H H NO 2 H Me 420 228 CO 2 Me H H H H Me 359 229 CO 2 Me H H H H Me 396 230 CO 2 Me H OH OH H Me 426 231 CO 2 Me H H F H Me 376 232 CO 2 Me H H NO 2 H Me 461 233 CO 2 Me H Cl Cl H Me 468 234 CO 2 Me H H H H Me 373 235 CO 2 Me H H H H Me 375 236 CO 2 Me H NO 2 H H Me 443 237 CO 2 Me H H NO 2 H Me 443 238 CO 2 Me H H H H Me 398 239 CO 2 Me H Cl Cl H Me 491 240 CO 2 Me H H H Me 509 241 CO 2 Me H H H Me 473 242 CO 2 Me H H H Me 509 243 CO 2 Me H H H H Me 310 244 CO 2 Me H H H Me 524 245 CO 2 Me H H H Me 488 246 CO 2 Me H H H H Me 308 247 CO 2 Me i-Pr H H H H Me 296 248 CO 2 Me H H H H Me 336 249 CO 2 Me Me H H H H Me 268 250 CO 2 Me H H H Me 474 251 CO 2 Me H H H Me 487 252 CO 2 Me N-Morpholino H H H H Me 339 253 CO 2 Me H H H H Me 337 254 CO 2 Me H H H Me 488 255 CO 2 Me H H H Me 474 256 CO 2 Me H H H Me 456 257 CO 2 Me H H H Me 431 258 CO 2 Me H H H Me 500 259 CO 2 Me H H H Me 499 260 CO 2 Me H H H Me 481 261 CO 2 Me H H H Me 500 262 CO 2 Me H H H Me 499 263 CO 2 Me H H H Me 431 264 CO 2 Me H H H H NH 2 397 (M + 23) 265 CO 2 Me H H H H NH 2 353 (M + 23) 266 CO 2 Me H H H H NH 2 413 (M + 23) 267 CO 2 Me 2-Furyl H H H H NH 2 321 268 CO 2 Me 3-Furyl H H H H NH 2 321 269 CO 2 Me 2-Furyl H H H H Me 320 270 CO 2 Me 2-Furyl H H H NH 2 Me 335 271 CO 2 Me 2-Furyl NHOH H H H Me 351 272 CO 2 Et 2-Furyl H H H H NH 2 335 273 CO 2 Et 2-Furyl H Br H H NH 2 413 274 CO 2 Et 2-Furyl H H Br H NH 2 413 275 CO 2 Et H H H H Me 467 276 CO 2 Me H H H Me 481 277 CO 2 Me H H H Me 456 278 CO 2 Me H H H Me 473 279 CO2Me H H H Me 513 280 CO 2 Me H H H Me 516 281 CO 2 Me H H H Me 501 282 CO 2 Me H H H Me 566 283 CO 2 Me H H H Me 488 284 CO 2 Me H H H Me 541
III. Biological Assays and Activity
Ligand Binding Assay for Adenosine A2a Receptor
[0151] Ligand binding assay of adenosine A2a receptor was performed using plasma membrane of HEK293 cells containing human A2a adenosine receptor (PerkinElmer, RB-HA2a) and radioligand [ 3 H]CGS21680 (PerkinElmer, NET1021). Assay was set up in 96-well polypropylene plate in total volume of 200 mL by sequentially adding 20 mL 1:20 diluted membrane, 130 mL assay buffer (50 mM Tris.HCl, pH7.4 10 mM MgCl 2 , 1 mM EDTA) containing [ 3 H] CGS21680, 50 mL diluted compound (4×) or vehicle control in assay buffer. Nonspecific binding was determined by 80 mM NECA. Reaction was carried out at room temperature for 2 hours before filtering through 96-well GF/C filter plate pre-soaked in 50 mM Tris.HCl, pH7.4 containing 0.3% polyethylenimine. Plates were then washed 5 times with cold 50 mM Tris.HCl, pH7.4., dried and sealed at the bottom. Microscintillation fluid 30 ml was added to each well and the top sealed. Plates were counted on Packard Topcount for [ 3 H]. Data was analyzed in Microsoft Excel and GraphPad Prism programs. (Varani, K.; Gessi, S.; Dalpiaz, A.; Borea, P. A. British Journal of Pharmacology, 1996, 117, 1693)
[0000] Adenosine A2a Receptor Functional Assay
[0152] CHO-K1 cells overexpressing human adenosine A2a receptors and containing cAMP-inducible beta-galactosidase reporter gene were seeded at 40-50K/well into 96-well tissue culture plates and cultured for two days. On assay day, cells were washed once with 200 mL assay medium (F-12 nutrient mixture/0.1% BSA). For agonist assay, adenosine A2a receptor agonist NECA was subsequently added and cell incubated at 37 C, 5% CO 2 for 5 hrs before stopping reaction. In the case of antagonist assay, cells were incubated with antagonists for 5 minutes at R.T. followed by additon of 50 nM NECA. Cells were then incubated at 37 C, 5% CO 2 for 5 hrs before stopping experiments by washing cells with PBS twice. 50 mL 1× lysis buffer (Promega, 5× stock solution, needs to be diluted to 1× before use) was added to each well and plates frozen at −20 C. For b-galactosidase enzyme colormetric assay, plates were thawed out at room temperature and 50 mL 2× assay buffer (Promega) added to each well. Color was allowed to develop at 37 C for 1 hr. or until reasonable signal appeared. Reaction was then stopped with 150 mL 1 M sodium carbonate. Plates were counted at 405 nm on Vmax Machine (Molecular Devices). Data was analyzed in Microsoft Excel and GraphPad Prism programs. (Chen, W. B.; Shields, T. S.; Cone, R. D. Analytical Biochemistry, 1995, 226, 349; Stiles, G. Journal of Biological Chemistry, 1992, 267, 6451)
[0000] Assay of Phosphodiesterase Activity
[0153] The assay of phosphodiesterase activity follows the homogeneous SPA (scintillation proximity assay) format under the principle that linear nucleotides preferentially bind yttrium silicate beads in the presence of zinc sulfate.
[0154] In this assay, the enzyme converts radioactively tagged cyclic nucleotides (reaction substrate) to linear nucleotides (reaction product) which are selectively captured via ion chelation on a scintillant-containing bead. Radiolabeled product bound to the bead surface results in energy transfer to the bead scintillant and generation of a quantifiable signal. Unbound radiolabel fails to achieve close proximity to the scintillant and therefore does not generate any signal.
[0155] Specifically, enzyme was diluted in PDE buffer (50 mM pH 7.4 Tris, 8.3 mM MgCl 2 , 1.7 mM EGTA) with 0.1% ovalbumin such that the final signal:noise (enzyme:no enzyme) ratio is 5-10. Substrate (2,8- 3 H-cAMP or 8- 3 H-cGMP, purchased from Amersham Pharmacia) was diluted in PDE (4, 5, 7A) buffer to 1 nCi per μl (or 1 μCi/ml). For each test well, 48 μl of enzyme was mixed with 47 μl substrate and 5 μl test compound (or DMSO) in a white Packard plate, followed by shaking to mix and incubation for 15 minutes at room temperature. A 50 μl aliquot of evenly suspended yttrium silicate SPA beads in zinc sulfate was added to each well to terminate the reaction and capture the product. The plate was sealed using Topseal-S (Packard) sheets, and the beads were allowed to settle by gravity for 15-20 minutes prior to counting on a Packard TopCount scintillation counter using a 3 H glass program with color quench correction. Output was in color quench-corrected dpm.
[0156] Test compounds were diluted in 100% DMSO to a concentration 20× final assay concentration. DMSO vehicle alone was added to uninhibited control wells. Inhibition (%) was calculated as follows:
Nonspecific binding ( NSB ) = the mean of CPM of the substrate + buffer + DMSO wells
Total Binding ( TB ) = the mean of the enzyme + substrate + DMSO wells
% i nhibition listed in Table 1 = ( 1 - ( Sample CPM - NSB ) TB - NSB ) × 100
[0157] The IC 50 values were calculated using the Deltagraph 4-parameter curve-fitting program. The IC 50 and % Inhibition data on PDE 4, 5, and 7A are listed for the indicated compounds in Table 2 below.
TABLE 2 Ia MS IC 50 (μM) / % inh.@μM No. R 1 R 2 R 3a R 3b R 3c R 3d R 4 (M + 1) PDE7A PDE4 PDE5 6 CO 2 H
C 7 H 5 O 2 H H H H Me 360 45% @20 49%@5 51 CO 2 Me
C 8 H 9 H H H H Me 358 0.055 0.353 2.7 56 CO 2 Et
C 7 H 5 O 2 H H NHAc H Me 445 0.074 0.333 2.5 70 CO 2 Et
C 8 H 9 H H H H i-Pr 400 2.11 73 CO 2 Me
C 8 H 9 H H H H Et 372 1.54 0.998 82 CO 2 Me
C 8 H 9 H NH 2 H H Me 373 0.021 0.204 1.11, 0.864 90 CO 2 Me
C 11 H 9 H NH2 H H Me 409 0.005 0.237, 0.172 2.33 98 CN
C 11 H 9 H H H H Me 361 1.13 119 CONHMe
C 11 H 9 H H H H Me 393 0.658 41% @20 133 Ac
C 6 H 3 Br 2 H H H H Me 472 1.54 134 Ac
C 8 H 9 H H H H Me 342 1.14 169 CO 2 Me
C 6 H 3 Br 2 O H H NO 2 H Me 551 0.0053 0.184 170 CO 2 Me
C 6 H 3 Br 2 O H Cl Cl H Me 573 0.0087 0.557 190 CO 2 H
C 6 H 3 Br 2 H Cl Cl H Me 544 5.9 191 CN
C 6 H 3 I 2 O H H H H Me 565 0.593 197 CO 2 Et
C 6 H 5 BrN H H H H Me 437 0.728 69% @5 0.362 219 CO 2 Me
C 7 H 8 N H H H H Me 359 0.964 61% @5 1.1 220 CO 2 Me —NHPh H H H H Me 345 0.084 1.8 0.637 241 CO 2 Me
C 8 H 9 H H
C 4 H 6 NO 3 H Me 473 0.0035 0.954 0.183 242 CO 2 Me
C 11 H 9 H H
C 4 H 6 NP 3 H Me 509 0.0038 0.782 0.141 243 CO 2 Me
C 4 H 9 H H H H Me 310 2.6 245 CO 2 Me
C 8 H 9 H H
C 4 H 7 N 2 O 3 H Me 488 0.0053 0.875 0.185 248 CO 2 Me
Cyclohexyl H H H H Me 336 0.783 0.171 0.649 250 CO 2 Me
C 8 H 9 H H
C 4 H 9 N 2 O 2 H Me 474 0.0074 0.684 2.4 251 CO 2 Me
C 8 H 9 H H
C 5 H 8 NO 3 H Me 487 0.0054 0.754 0.26 253 CO 2 Me
C 5 H 10 N H H H H Me 337 0.905 0.85 0.303 254 CO 2 Me
C 8 H 9 H H
C 5 H 11 N 2 O 2 H Me 488 0.0067 0.664 0.765 261 CO 2 Me
C 8 H 9 H H H Me 500 0.0063 0.477 0.63 262 CO 2 Me
C 8 H 9 H H
C 6 H 12 N 3 O H Me 499 0.008 0.702 3.7
[0158]
TABLE 3
Ia
Ki (nM)
A2a
A2a
antago-
A1
MS
bind-
nist
bind-
No.
R 1
R 2
R 3a
R 3b
R 3c
R 3d
R 4
(M + 1)
ing
function
ing
14
CO 2 Et c 6 h 4 BrO 2
H
H
H
H
Me
454
451
22
CO 2 Et
C 7 H 5 O 2
H
H
H
H
NH 2
411 (M +23)
70
253
18
CO 2 Me
C 7 H 5 O 2
H
H
H
H
Me
374
159
>1000
584
27
CO 2 Et
Ph
H
H
H
H
NH 2
345
42
36
554
23
CO 2 Et
C 7 H 5 O 2
H
H
H
H
Me
388
251
275
CO 2 Et
C 7 H 4 BrO 2
H
H
H
H
Me
467
263
41
CO 2 Et
C 4 H 3 O
H
H
H
H
Me
334
271
57
CO 2 Et
C 7 H 7
H
H
H
H
Me
358
400
67
CO 2 Me
C 7 H 7
H
H
H
H
Me
344
39
128
1853
66
CO 2 Me
C 7 H 7
H
H
H
H
Me
344
46
151
1591
85
CO 2 Me
C 6 H 4 Br
H
H
H
H
Me
431 (M +23)
35
>1000
5570
82
CO 2 Me
C 8 H 9
H
NH 2
H
H
Me
373
294
95
CO 2 Me
C 11 H 9
H
H
H
H
NH 2
395
286
135
CO 2 Me
C 5 H 4 N
H
H
H
H
Me
331
123
130
CO 2 Me
C 6 H 6 N
H
H
H
H
Me
345
222
141
CO 2 Me
C 6 H 5 O
H
H
H
H
Me
346
172
183
CO 2 Et
C 8 H 10 N
H
H
H
H
Me
387
191
208
CO 2 Me
C 7 H 4 N
H
H
H
H
Me
355
171
197
CO 2 Et
C 6 H 5 BrN
H
H
H
H
Me
437
148
217
CO 2 Me
C 7 H 6 F
H
H
H
H
Me
362
119
221
CO 2 Me
C 6 H 5 BrN
H
H
H
H
Me
423
76
258
2180
222
CO 2 Me
2-Pyridyl
H
H
H
H
Me
353 (M +23)
237
198
CO 2 Et
C 7 H 8 NO
H
H
H
H
Me
389
185
199
CO 2 Et
C 6 H 3 I 2 O
H
H
H
H
Me
612
301
279
CO 2 Me
C 8 H 9
H
H
H
Me
513
179
261
CO 2 Me
C 8 H 9
H
H
C 6 H 11 N 2 O 2
H
Me
500
472
280
CO 2 Me
C 8 H 9
H
H
H
Me
516
237
276
CO 2 Me
C 8 H 9
H
H
C 5 H 6 N 3 O
H
Me
481
304
258
CO 2 Me
C 8 H 9
H
C 6 H 11 N 2 O 2
H
H
Me
500
211
281
CO 2 Me
C 8 H 9
H
H
H
Me
501
201
262
CO 2 Me
C 8 H 9
H
H
C 6 H 12 N 3 O
H
Me
499
332
184
CO 2 Et
C 7 H 8 N
H
H
H
H
Me
373
140
195
CO 2 Et
C 6 H 4 Cl 2 N
H
H
H
H
Me
427
171
260
CO 2 Me
C 8 H 9
H
C 5 H 6 N 3 O
H
H
Me
481
163
263
CO 2 Me
C 8 H 9
H
H
C 2 H 4 NO 2
H
Me
431
480
245
CO 2 Me
C 8 H 9
H
H
C 4 H 7 N 2 O 3
H
Me
488
276
264
CO 2 Me
C 7 H 5 O 2
H
H
H
H
NH 2
397 (M +23)
342
265
CO 2 Me
Ph
H
H
H
H
NH 2
353 (M +23)
50
267
CO 2 Me
2-Furyl
H
H
H
H
NH 2
321
<15
268
CO 2 Me
3-Furyl
H
H
H
H
NH 2
321
21
269
CO 2 Me
H
H
H
H
Me
320
192
270
CO 2 Me
2-Furyl
H
H
H
NH 2
Me
335
303
271
CO 2 Me
2-Furyl
NH OH
H
H
H
Me
351
276
272
CO 2 Et
2-Furyl
H
H
H
H
NH 2
335
<5
273
CO 2 Et
2-Furyl
H
Br
H
H
NH 2
413
279
274
CO 2 Et
2-Furyl
H
H
Br
H
NH 2
413
143
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This invention provides novel arylindenopyridines of the formula:
and pharmaceutical compositions comprising same, useful for treating disorders ameliorated by antagonizing Adensine A2a receptors or reducing PDE activity in appropriate cells. This invention also provides therapeutic and prophylactic methods using the instant pharmaceutical compositions.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This patent application is a non-provisional patent application of U.S. provisional patent application 61/467,323 filed on Mar. 24, 2011 and entitled “Quinoxaline Compounds and Derivatives”, and U.S. provisional patent application 61/467,335 filed on Mar. 24, 2011 and entitled “Aromatic Neuroprotecting Compounds and Derivatives Thereof” the content of each of which is hereby incorporated by reference in its entirety.
STATEMENT OF FEDERALLY FUNDED RESEARCH
Not Applicable.
SEQUENCE LISTING
Not Applicable.
INCORPORATION-BY-REFERENCE OF MATERIALS FILED ON COMPACT DISC
Not Applicable.
TECHNICAL FIELD OF THE INVENTION
The present invention relates in general to the field of pharmaceutical compositions and synthesis, and more particularly, to novel compositions and methods for preparing the compound and its pharmaceutical use.
BACKGROUND OF THE INVENTION
U.S. Patent Application Publication No. 2009/0286797, entitled, Novel Quinoxaline Derivatives and Their Medical Use discloses novel quinoxaline derivatives having medical utility, to use of the quinoxaline derivatives of the invention for the manufacture of a medicament, to pharmaceutical compositions comprising the quinoxaline derivatives of the invention, and to methods of treating a disorder, disease or a condition of a subject, which disorder, disease or condition is responsive to positive modulation of AMPA receptor mediated synaptic responses.
U.S. Pat. No. 3,759,912, entitled, Quinoxalines discloses a Quinoxaline useful as broad spectrum antimicrobials in human and veterinary medicine; novel intermediates useful in their preparation; processes for their production from the appropriate quinoxaline, N-monoxide quinoxaline, quinoxaline carboxylic acid or furazan oxide are disclosed.
BRIEF SUMMARY OF THE INVENTION
The present invention provides a compound of formula or pharmaceutical salts thereof:
wherein A and B are selected from C, N, S, O. R 1 -R 7 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester, group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. R 8 is a C 1 -C 6 Alkyl group, a C 1 -C 6 alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an ether group, an ester group, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. R 9 -R 13 are independently selected from a H, a C 1 -C 6 Alkyl; a C 1 -C 6 Alkenyl, a halo, a substituted C 1 -C 6 alkyl, a substituted C 1 -C 6 alkenyl, a carbonyl, a carbonate ester, an acetoxy group, a an acetyl group, an ether, an ester, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group.
The present invention provides a compound of formula or pharmaceutical salts thereof:
wherein R 1 -R 13 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group.
A compound of formula or pharmaceutical salts thereof:
wherein R 1 -R 6 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. R 7 -R 16 are independently selected from a H, a C 1 -C 6 Alkyl; a C 1 -C 6 Alkenyl, a halo, a substituted C 1 -C 6 alkyl, a substituted C 1 -C 6 alkenyl, a carbonyl, a carbonate ester, an acetoxy group, a an acetyl group, an ether, an ester, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group.
A compound of formula or pharmaceutical salts thereof:
wherein R 1 -R 11 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group.
A compound of formula or pharmaceutical salts thereof:
wherein A, A′, B and B′ are selected from C, N, S, O. R 2 -R 10 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group.
DETAILED DESCRIPTION OF THE INVENTION
While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention.
To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims.
The term “alkyl”, “alkenyl”, “alkynyl” and “alkylene” denotes hydrocarbon chains typically ranging from about 1 to about 12 carbon atoms in length, preferably 1 to about 6 atoms, and includes straight and branched chains. Unless otherwise noted, the preferred embodiment of any alkyl or alkylene referred to herein is C1-C6 alkyl (e.g., methyl or ethyl).
The term “cycloalkyl” denotes a saturated or unsaturated cyclic hydrocarbon chain, including bridged, fused, or spiro cyclic compounds, preferably comprising 3 to about 12 carbon atoms, more preferably 3 to about 8.
The term “aryl” denotes one or more aromatic rings, each of 5 or 6 core carbon atoms. Multiple aryl rings may be fused, as in naphthyl or unfused, as in biphenyl. Aryl rings may also be fused or unfused with one or more cyclic hydrocarbon, heteroaryl, or heterocyclic rings.
The term “heteroaryl” denotes an aryl group containing from one to four heteroatoms, preferably N, O, or S, or a combination thereof, which heteroaryl group is optionally substituted at carbon or nitrogen atom(s) with C1-C6 alkyl, —CF3, phenyl, benzyl, or thienyl, or a carbon atom in the heteroaryl group together with an oxygen atom form a carbonyl group, or which heteroaryl group is optionally fused with a phenyl ring. Heteroaryl rings may also be fused with one or more cyclic hydrocarbon, heterocyclic, aryl, or heteroaryl rings. Heteroaryl includes, but is not limited to, 5-membered heteroaryls having one hetero atom (e.g., thiophenes, pyrroles, furans); 5-membered heteroaryls having two heteroatoms in 1,2 or 1,3 positions (e.g., oxazoles, pyrazoles, imidazoles, thiazoles, purines); 5-membered heteroaryls having three heteroatoms (e.g., triazoles, thiadiazoles); 5-membered heteroaryls having 3 heteroatoms; 6-membered heteroaryls with one heteroatom (e.g., pyridine, quinoline, isoquinoline, phenanthrine, 5,6-cycloheptenopyridine); 6-membered heteroaryls with two heteroatoms (e.g., pyridazines, cinnolines, phthalazines, pyrazines, pyrimidines, quinazolines); 6-membered heteroaryls with three heteroatoms (e.g., 1,3,5-triazine); and 6-membered heteroaryls with four heteroatoms.
The term “heterocycle” or “heterocyclic” denotes one or more rings of 5-12 atoms, preferably 5-7 atoms, with or without unsaturation or aromatic character and at least one ring atom which is not carbon. Preferred heteroatoms include sulfur, oxygen, and nitrogen. Multiple rings may be fused.
The term “heteroatom” denotes any non-carbon atom in a hydrocarbon analog compound. Examples include oxygen, sulfur, nitrogen, phosphorus, arsenic, silicon, selenium, tellurium, tin, and boron.
The term “alkylene” denotes a divalent alkyl group as defined above, such as methylene (—CH 2 —), propylene (—CH 2 CH 2 CH 2 —), chloroethylene (—CHClCH 2 —), 2-thiobutene —CH 2 CH(SH)CH 2 CH 2 , 1-bromo-3-hydroxyl-4-methylpentene (—CHBrCH 2 CH(OH)CH(CH 3 )CH 2 —), and the like.
The term “alkenyl” denotes branched or unbranched hydrocarbon chains containing one or more carbon-carbon double bonds.
The term “alkynyl” denotes branched or unbranched hydrocarbon chains containing one or more carbon-carbon triple bonds.
The term “aryl” denotes a chain of carbon atoms which form at least one aromatic ring having preferably between about 6-14 carbon atoms, such as phenyl, naphthyl, and the like, and which may be substituted with one or more functional groups which are attached commonly to such chains, such as hydroxyl, bromo, fluoro, chloro, iodo, mercapto or thio, cyano, cyanoamido, alkylthio, heterocycle, aryl, heteroaryl, carboxyl, carbalkoyl, alkyl, alkenyl, nitro, amino, alkoxyl, amido, and the like to form aryl groups such as biphenyl, iodobiphenyl, methoxybiphenyl, anthryl, bromophenyl, iodophenyl, chlorophenyl, hydroxyphenyl, methoxyphenyl, formylphenyl, acetylphenyl, trifluoromethylthiophenyl, trifluoromethoxyphenyl, alkylthiophenyl, trialkylammoniumphenyl, amidophenyl, thiazolylphenyl, oxazolylphenyl, imidazolylphenyl, imidazolylmethylphenyl, and the like.
The term “alkoxy” denotes —OR—, wherein R is alkyl.
The term “amido” denotes an amide linkage: —C(O)NHR (wherein R is hydrogen or alkyl).
The term “amino” denotes an amine linkage: —NR—, wherein R is hydrogen or alkyl. The term “carboxyl” denotes —C(O)O—, and the term “carbonyl” denotes —C(O)—.
The term “alkylcarboxyl” denote an alkyl group as defined above substituted with a C(O)O group, for example, CH 3 C(O)O—, CH 3 CH 2 C(O)O—, etc.
The term “carbocycle” denotes cyclic hydrocarbon chain having about 5 to about 8 ring carbons such as cyclopentyl, cylcohexyl, etc. These groups can be optionally substituted with one or more functional groups as defined under “alkyl” above.
The term “halogen” includes chlorine, fluorine, bromine, iodine and mixtures thereof.
The term “heterocycle” denotes straight chain or ring system that may contain from zero to four heteroatoms selected from N, O, and S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized.
The term “carbamoyl” denotes the group —C(O)NH 2 .
The term “hydroxyalkyl” denotes an alkyl group as defined above which is substituted by a hydroxy group.
The term “alkylcarboxyl”, alone or in combination, means an acyl group derived from an alkanecarboxylic acid, i.e. alkyl-C(O)—, such as acetyl, propionyl, butyryl, valeryl, 4-methylvaleryl etc.
The present invention provides compound of the general formula:
wherein a, b, and c are selected from C, N, S, O. R 1 -R 7 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. R 8 is a C 1 -C 6 Alkyl group, a C 1 -C 6 alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an ether group, an ester group, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. R 9 -R 13 are independently selected from a H, a C 1 -C 6 Alkyl; a C 1 -C 6 Alkenyl, a halo, a substituted C 1 -C 6 alkyl, a substituted C 1 -C 6 alkenyl, a carbonyl, a carbonate ester, an acetoxy group, a an acetyl group, an ether, an ester, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group.
The present invention provides compound of the general formula:
wherein R 2 -R 6 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. R 8 is a C 1 -C 6 Alkyl group, a C 1 -C 6 alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an ether group, an ester group, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. R 9 -R 13 are independently selected from a H, a C 1 -C 6 Alkyl; a C 1 -C 6 Alkenyl, a halo, a substituted C 1 -C 6 alkyl, a substituted C 1 -C 6 alkenyl, a carbonyl, a carbonate ester, an acetoxy group, a an acetyl group, an ether, an ester, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. For example,
The present invention provides compound of the general formula:
wherein R 2 -R 6 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. R 8 is a C 1 -C 6 Alkyl group, a C 1 -C 6 alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an ether group, an ester group, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. R 9 -R 16 are independently selected from a H, a C 1 -C 6 Alkyl; a C 1 -C 6 Alkenyl, a halo, a substituted C 1 -C 6 alkyl, a substituted C 1 -C 6 alkenyl, a carbonyl, a carbonate ester, an acetoxy group, a an acetyl group, an ether, an ester, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. For example,
The present invention provides compound of the general formula:
wherein R 2 -R 11 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example,
The present invention provides compound of the general formula:
wherein A, A′, B and B′ are selected from C, N, S, O. R 2 -R 10 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example:
The present invention provides (Z)-6,7-dimethyl-3-(2-oxo-2-phenylethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-7-chloro-3-(2-oxo-2-phenylethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-7-fluoro-3-(2-oxo-2-phenylethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(2-(4-methoxyphenyl)-2-oxoethylidene)-6,7-dimethyl-3,4-dihydroquinoxalin-2(1H)-one; (Z)-6,7-dichloro-3-(2-(4-methoxyphenyl)-2-oxoethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-7-chloro-3-(2-(4-methoxyphenyl)-2-oxoethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-7-fluoro-3-(2-(4-methoxyphenyl)-2-oxoethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-oxo-2-(2-oxo-2-phenylethylidene)-1,2,3,4-tetrahydroquinoxaline-6-carbonitrile; (Z)-7-bromo-3-(2-(4-methoxyphenyl)-2-oxoethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-oxo-2-(2-oxo-2-phenylethylidene)-1,2,3,4-tetrahydroquinoxaline-6-carbonitrile; (Z)-7-bromo-3-(2-(4-methoxyphenyl)-2-oxoethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-5-hydroxy-3-(2-oxo-2-phenylethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-5-hydroxy-3-(2-(4-methoxyphenyl)-2-oxoethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-methyl3-oxo-2-(2-oxo-2-phenylethylidene)-1,2,3,4-tetrahydroquinoxaline-6-carboxylate; (Z)-methyl2-(2-(4-methoxyphenyl)-2-oxoethylidene)-3-oxo-1,2,3,4-tetrahydroquinoxaline-6-carboxylate; (Z)-methyl3-oxo-2-(2-oxo-2-(4-(trifluoromethyl)phenyl)ethylidene)-1,2,3,4-tetrahydroquinoxaline-6-carboxylate; (Z)-3-(2-(4-(benzyloxy)phenyl)-2-oxoethylidene)-7-bromo-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(2-(4-methoxyphenyl)-2-oxoethylidene)-7-methyl-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(2-(3,5-dibromo-4-hydroxyphenyl)-2-oxoethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(2-(3,5-dibromo-4-hydroxyphenyl)-2-oxoethylidene)-7-nitro-3,4-dihydroquinoxalin-2(1H)-one; (Z)-6,8-dibromo-3-(2-(3,5-dibromo-4-hydroxyphenyl)-2-oxoethylidene)-7-hydroxy-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(2-(3,5-dibromo-4-hydroxyphenyl)-2-oxoethylidene)-5-hydroxy-3,4-dihydroquinoxalin-2(1H)-one; (Z)-7-bromo-3-(2-(3,5-dibromo-A-hydroxyphenyl)-2-oxoethylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(3,5-dibromo-4-hydroxybenzylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(3,5-dibromo-4-hydroxybenzylidene)-7-methoxy-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(3,5-dibromo-4-hydroxybenzylidene)-6,7-dimethyl-3,4-dihydroquinoxalin-2(1H)-one; (Z)-6,7-dichloro-3-(3,5-dibromo-4-hydroxybenzylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-7-chloro-3-(3,5-dibromo-4-hydroxybenzylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(3,5-dibromo-4-hydroxybenzylidene)-7-fluoro-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-((1H-pyrrol-2-yl)methylene)-6,7-dimethyl-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-(3,5-dibromobenzyl idene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-6-chloro-3-(3,5-dibromobenzylidene)-3,4-dihydroquinoxalin-2(1H)-one; (Z)-3-((1H-pyrrol-2-yl)methylene)-6-chloro-3,4-dihydroquinoxalin-2(1H)-one; (Z)-6-chloro-3-(furan-2-ylmethylene)-3,4-dihydroquinoxalin-2(1H)-one; and (Z)-7-bromo-3-(furan-2-ylmethylene)-3,4-dihydroquinoxalin-2(1H)-one.
The present invention provides compound of the general formula:
wherein A, A′, B, B′ and C are selected from C, N, S, O. R 1 -R 7 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. R 8 is a C 1 -C 6 Alkyl group, a C 1 -C 6 alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an ether group, an ester group, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. R 9 -R 13 are independently selected from a H, a C 1 -C 6 Alkyl; a C 1 -C 6 Alkenyl, a halo, a substituted C 1 -C 6 alkyl, a substituted C 1 -C 6 alkenyl, a carbonyl, a carbonate ester, an acetoxy group, a an acetyl group, an ether, an ester, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group.
The present invention provides compound of the general formula:
wherein A′, and B′ are selected from C, N, S, O. R 2 -R 6 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. R 8 is a C 1 -C 6 Alkyl group, a C 1 -C 6 alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an ether group, an ester group, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. R 9 -R 13 are independently selected from a H, a C 1 -C 6 Alkyl; a C 1 -C 6 Alkenyl, a halo, a substituted C 1 -C 6 alkyl, a substituted C 1 -C 6 alkenyl, a carbonyl, a carbonate ester, an acetoxy group, a an acetyl group, an ether, an ester, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group.
The present invention provides compound of the general formula:
wherein A′, and B′ are selected from C, N, S, O. R 2 -R 4 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. R 8 is a C 1 -C 6 Alkyl group, a C 1 -C 6 alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an ether group, an ester group, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. R 9 -R 13 are independently selected from a H, a C 1 -C 6 Alkyl; a C 1 -C 6 Alkenyl, a halo, a substituted C 1 -C 6 alkyl, a substituted C 1 -C 6 alkenyl, a carbonyl, a carbonate ester, an acetoxy group, a an acetyl group, an ether, an ester, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group.
For example,
The present invention provides compound of the general formula:
wherein R 2 -R 4 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. R 8 is a C 1 -C 6 Alkyl group, a C 1 -C 6 alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an ether group, an ester group, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. R 9 -R 12 are independently selected from a H, a C 1 -C 6 Alkyl; a C 1 -C 6 Alkenyl, a halo, a substituted C 1 -C 6 alkyl, a substituted C 1 -C 6 alkenyl, a carbonyl, a carbonate ester, an acetoxy group, an acetyl group, an ether, an ester, an alkyl alkanoate group, an alkoxy group, a keto group, and an oxo group. For example,
Dihydroquinoxalin derivative compounds or pharmaceutical salts thereof:
and more specifically
wherein R 1 -R 8 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example:
IC 50
Code
structure
Value
SK-C-7
2.51
SK-C-11
4.3
A compound of formula or pharmaceutical salts thereof:
wherein A and B are individually a C, O, N or S and R1 is an alkyl or an alkenyl and R2 is a phenyl, benzyloxyl, pyridyl, indolone, pyrrol, carbamoyl, pyridine, substituted phenyl, substituted benzyloxyl, substituted pyridine, or substituted pyridyl and R3 is a hydrogen, a halogen, an amino, an alkyl or an alkenyl.
A compound of formula or pharmaceutical salts thereof:
wherein A and B are individually a C, O, N or S and R 1 -R 10 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example,
A compound of formula or pharmaceutical salts thereof:
wherein A and B are individually a C, O, N or S and R 1 -R 8 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example:
A compound of formula or pharmaceutical salts thereof:
wherein A and B are individually a C, O, N or S and R 1 -R 8 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example:
A compound of formula or pharmaceutical salts thereof:
wherein A and B are individually a C, O, N or S and R 1 -R 8 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example:
A compound of formula or pharmaceutical salts thereof:
wherein A and B are individually a C, O, N or S and R 1 -R 8 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example:
Hydrazono-indolin-2-one derivative compounds or pharmaceutical salts thereof:
wherein R 1 -R 8 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example:
Code
structure
IC 50 Value
SK-HIBS-1
2.70
SK-MH—Cl—Br—OH
1.67
SK-MH—Cl-diCl—OH
3.3
SK-MH-Cl—CN
1.56348
SK-MH-diBr
0.182779
Pyrimidine derivative compounds or pharmaceutical salts thereof:
wherein R 1 -R 3 are independently selected from a H, a C 1 -C 6 Alkyl group, a C 1 -C 6 Alkenyl group, a halo group, a substituted C 1 -C 6 alkyl group, a substituted C 1 -C 6 alkenyl group, a carbonyl group, a carbonate ester group, an C 1 -C 6 ether group, an C 1 -C 6 ester group, an C 1 -C 6 alkyl alkanoate group, an C 1 -C 6 alkoxy group, a keto group, and an oxo group. For example:
Code
structure
IC 50 Value
SK-Barbi-diBr
0.741839
SK-Barbi-DiCl
0.310457
It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method, kit, reagent, or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention.
It will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims.
All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.
The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.” Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.
As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.
The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, MB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.
All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.
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The present invention provides oxazine compounds, method of using and method of making oxazine compounds and its pharmaceutical use.
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FIELD OF INVENTION
[0001] The present invention relates to 8-hydroxyjulolidine and its analogous compounds and preparation thereof, especially to a one-step cyclization reaction of 3-aminophenol or 1,3-dihydroxyaniline with 1,3-dihalopropane or its analogs to prepare the desired julolidines. The 8-hydroxyjulolidine and its analogous compounds have the following chemical structure:
[0002] wherein R 1 and R 2 represent independently hydrogen, halogen, hydroxyl group or alkyl groups.
BACKGROUND OF INVENTION
[0003] Coumarins are often used as lasing dyes and fluorescent probes in bioassays, because they exhibit the beneficial properties of tunable wavelengths, high quantum yields, high absorption coefficient and little overlapping in the absorption and emission spectra. According to U.S. Pat. No. 3,873,940, U.S. Pat. No. 3,932,415, U.S. Pat. No. 4,005,092 , U.S. Pat. No. 4,471,041 U.S. Pat. No. 4,736,032 and U.S. Pat. No. 4,794,184, coumarin compounds with fused and rigid nitrogen-containing rings significantly hinder the mobility of amino groups and thus reduce the energy dissipation caused by the rotation of uncyclized amino groups. Such rigid coumarins also greatly increase the dipolar moments in the excited states, and thus attain high quantum yields and emission efficiencies in lasing.
[0004] However, there are only a few methods for the preparation of 8-hydroxyjulolidine and 8,1 0-dihydroxyjulolidine have been disclosed. In the conventional art, method for the preparation of these compounds, such as those disclosed in U.S. Pat. No. 4,005,092 , U.S. Pat. No. 4,471,041 and Journal of Organic Chemistry (1987) Vol. 52, pp. 1465-1468, 8-hydroxyjulolidine and 8,1 0-dihydroxyjulolidine are prepared by cyclization of m-anisidine (or 3,5-dimethoxyaniline) with excess amounts of 1-bromo-3-chloropropane, followed by demethylation with strong acids. Using dimethyl sulfate for methylations of 3-aminophenol and 3,5-dihydroxyaniline is generally carried out to obtain m-anisidine and 3,5-dimethoxyaniline.
[0005] The above-mentioned methods have several disadvantages. First, in the mass production of 8-hydroxyjulolidine or 8,1 0-dihydroxyjulolidine, excess 1-bromo-3-chloropropane (7.6-15 molar proportions) is used. Such an approach will bring out relatively higher production costs. Secondly, in the step of demethylation corrosive strong acids such as hydrochloric acid, hydroiodic acid and boron tribromide are needed. These materials are hazardous to the environment. Thirdly, the overall yields in the above-said approaches are low (<30%) due to the need of two extra steps, prior protection of the hydroxyl group with a toxic reagent of dimethyl sulfate and removal of the protecting methyl group after the cyclization reaction.
[0006] It is thus necessary to provide a novel method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein preparation costs may be reduced.
[0007] It is also necessary to provide a method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein no hazardous material is needed.
[0008] It is also necessary to provide a method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein yields of preparation may be improved.
[0009] It is also necessary to provide a simplified method for the preparation of 8-hydroxyjulolidine and its analogous compounds.
OBJECTIVES OF INVENTION
[0010] The objective of this invention is to provide a simplified method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein only one single step reaction is needed.
[0011] Another objective of this invention is to provide a novel method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein preparation costs may be reduced.
[0012] Another objective of this invention is to provide a method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein no hazardous material is needed.
[0013] Another objective of this invention is to provide a method for the preparation of 8-hydroxyjulolidine and its analogous compounds wherein yields of preparation may be improved.
SUMMARY OF INVENTION
[0014] According to this invention, a novel method for the preparation of 8-hydroxyjulolidine and its analogous compounds is disclosed. In the invented method, desired julolidines may be easily prepared by a single-step cyclization reaction, without the need of steps such as prior protection of hydroxyl groups or removal of the methyl groups. The invented method discloses an alkylative cyclization reaction at the amino group of the reactant whereby the hydroxyl group of the reactant will not be affected. As a result, yield of the invented method may be higher than that of the conventional method. The invented method comprises the following chemical reactions:
[0015] wherein X and Y represent independently halogen, acyloxyl, sulfonyloxyl or phosphoryloxyl group, and R 1 and R 2 represent independently H, halogen, hydroxyl, or alkyl group. In the reaction solution, an organic alkali, an inorganic alkali or a phase-transfer agent may be added. Suitable additives include triethylamine, LiOH, Na 2 CO 3 , NaHCO 3 , organic ammonium salts and organic sulfonates.
[0016] The products of this invention have the following structure:
[0017] wherein R 1 and R 2 are defined as above.
[0018] The invented method comprises a cyclization reaction of 3-aminophenol or 1,3-dihydroxyaniline with 1,3-dihalopropane or its analogs.
[0019] This invention also discloses a method of recrystallization or a solid-liquid continuous extraction of 8-hydroxyjulolidine and its analogous compounds to obtain purified products.
[0020] This invention also discloses a method for the preparation of various coumarins by further treatment of the resulting 8-hydroxyjulolidine and its analogs with appropriate reagents such as malonate and acetoacetate. This invention also discloses the products and intermediates prepared therefrom.
DETAILED DESCRIPTION OF INVENTION
[0021] In order to illustrate the features and advantages of this invention, the following embodiments are given as examples.
Embodiment 1: Synthesis of 8-Hydroxyjulolidine
[0022] m-Aminophenol (110 mg, 1 mmol), 1-bromo-3-chloropropane (2.35 g, 1.6 ml, 15 mmol) and anhydrous Na 2 CO 3 (212 g, 2 mmol) were placed in a 100 ml two-necked round-bottomed flask equipped with a thermometer and an addition funnel containing molecular sieves (4Å, 0.3 g). The top of the funnel was fitted with a condenser. Under an atmosphere of nitrogen, the mixture was heated to 70° C. for 3 hours and then refluxed at 110° C. for 15 hours. The resulting red mixture was cooled to room temperature and concentrated HCI solution (15 ml) was slowly added with care. After addition of CH 2 Cl 2 (5 ml), the aqueous layer was separated. The aqueous phase was neutralized by the addition of 40% NaOH aqueous solution and extracted with CH 2 Cl 2 (50 ml×4). The CH 2 Cl 2 extracts were combined, washed with brine, dried over anhydrous MgSO 4 and concentrated in reduced pressure. The crude product was subjected to silica gel column chromatography by elution with EtOAc/hexane (1:9) to give pure compound of 8-hydroxjulolidine (72 mg, 0.38 mmol) in 38% yield.
[0023] Colorless crystals were obtained by recrystallization from hexane. M.p.: 128-130° C. (literature value 126-128° C.). TLC (EtOAc/bexane, 1:9) R f =0.23. 1 H NMR (CDCl 3 , 300 MHz): δ1.94-1.99 (4 H, m), 2.62-2.70 (4 H, m), 3.04-3.12 (4 H, m), 4.43 (1 H.s), 6.04 (1 H, d, J=7.9 Hz), 6.64 (1 H, d, J=7.9 Hz).
Embodiment 2: Synthesis OF 8-Hydroxyjuloldine
[0024] According to a procedure similar to that of Embodiment 1, a mixture of m-aminophenol(1.1 g, 10 mmol), 1-bromo-3-chloropropane (23.5 g, 16 ml, 150 mmol) and anhydrous Na 2 CO 3 (4.27 g, 40 mmol) was heated and stirred at 70° C. for 3 hours and refluxed at 110° C. for 15 hours. After silica gel column chromatography 8-hydroxyjulolidine (800 mg) was obtained in 42% yield.
Embodiment 3: Synthesis OF 8-Hydroxyjulolidine
[0025] According to a procedure similar to that of Embodiment 1, a mixture of m-aminophenol (11.0 g, 101 mmol), 1 -bromo-3-chloropropane (127.4 g, 80 ml, 809 mmol) and anhydrous Na 2 CO 3 (42.4 g, 400 mmol) was heated and stirred at 70° C. for 3 hours and refluxed at 110° C. for 15 hours. After silica gel column chromatography, 8-hydroxyjulolidine (7.3 g) was obtained in 38% yield.
Embodiment 4: Synthesis of 8-Hydroxyjulolidine
[0026] According to a procedure similar to that of Embodiment 1, a mixture of m-aminophenol (5.0 g, 46 mmol), 1-bromo-3-chloropropane (23.9 g, 15 ml, 151 mmol) and N,N-dimethylformamide (15 ml) was heated and refluxed for 15 hours. After silica gel column chromatography, 8-hydroxyjulolidine (5.5 g) was obtained in 62% yield.
EXAMPLE 5
Synthesis of 8-Hydroxyjulolidine
[0027] m-Aminophenol (1.1 g, 10 mmol), 1-bromo-3-chloropropane (4.8 g, 3 ml, 30 mmol) and ethanol (10 ml) were placed in a 100 ml two-necked round-bottomed flask. The mixture was heated and refluxed for 11 hours, during which an NaHCO 3 aqueous solution (2.0 g, 20 ml, 23 mmol) was added. The mixture was further heated and refluxed for 37 hours. The solvent was removed by distillation under reduced pressure. The resulting crude product was extracted with hexane by a solid-liquid continuous extraction to give 8-hydroxyjulolidine (661 mg) in 35% yield.
Embodiment 6: Synthesis of 8-Hydroxyjulolidine
[0028] According to a procedure similar to that of Embodiment 5, a mixture of m-aminophenol (5.0 g, 45.8 mmol), 1-bromo-3-chloropropane (23.9 g, 15 ml, 150 mmol) and ethanol (50 ml) was heated and refluxed. NaHCO 3 (10.0 g, 119 mmol) aqueous solution (20 ml) was added slowly. After 24 hours of reflux, 3.4 g of 8-hydroxyjulolidine was obtained in 39% yield.
Embodiment 7: Synthesis of 8-Hydroxyjulolidine
[0029] According to a procedure similar to that of Embodiment 1, a mixture of m-aminophenol (110 mg, 1 mmol), 1-bromo-3-chloropropane (0.48 g, 0.3 ml, 3 mmol), sodium dihydrogen phosphate dihydrate (NaH 2 PO 4 .2H 2 O, 623 mg, 4 mmol) and water (10 ml) was heated and refluxed for 12 hours. After silica gel column chromatography, 8-hydroxyjulolidine (30 mg) was obtained in 16% yield.
Embodiment 8: Synthesis of 8-Hydroxyjulolidine
[0030] According to a procedure similar to that of Embodiment 1, a mixture of m-aminophenol (115 mg, 1 mmol), 1-bromo-3-chloropropane (0.48 g, 0.3 ml, 3 mmol) and a buffer solution prepared by dissolving 1.50 g (4 mmol) of disodium hydrogen phosphate decahydrate (Na 2 HPO 4 .12H 2 O) and 0.60 g (4 mmol) of NaH 2 PO 4 .2H 2 O in 10 ml water was heated and refluxed for 24 hours. After silica gel column chromatography, 8-hydroxyjulolidine (40 mg) was obtained in 21% yield.
Embodiment 9: Synthesis of 8-Hydroxyjulolidine
[0031] According to a procedure similar to that of Embodiment 1, a mixture of m-aminophenol (116 mg, 1 mmol), 1-bromo-3-chloropropane (0.48 g, 0.3 ml, 3 mmol), dodecylbenzenesulfonic acid sodium salt (349 mg, 1 mmol) and a buffer solution prepared by dissolving 1.50 g (4 mmol) of Na 2 HPO 4 ,12H 2 O and 0.60 g (4 mmol) of NaH 2 PO 4 .2H 2 O in water (10 ml) was heated and refluxed for 12 hours. After silica gel column chromatography, 8-hydroxyjulolidine (28 mg) was obtained in 15% yield.
Embodiment 10: Synthesis of 8-Hydroxyjulolidine
[0032] According to a procedure similar to that of Embodiment 1, a mixture of m-aminophenol (110 mg, 1 mmol), 1,3-bis(toluenesulfonyloxy)propane (3.84 g, 10 mmol), wet 1,4-dioxane (3 ml) and anhydrous Na 2 CO 3 (424 mg, 4 mmol) was heated and refluxed for 5 days. After silica gel column chromatography, 8-hydroxyjulolidine (51 mg) was obtained in 27% yield.
Embodiment 11: Synthesis of 8.1 0-Dihydroxyjulolidine
[0033] According to a procedure similar to that of Embodiment 1, a mixture of 3,5-dihydroxyaniline(1.30 g, 10 mmol), 1-bromo-3-chloropropane (4.77 g, 3 ml, 30 mmol) and N,N-dimethylformamide (10 ml) was heated and refluxed for 5 hours. After silica gel column chromatography, 8,10-dihydroxyjulolidine (617 mg) was obtained in 30% yield. The product is not stable and will turn from colorless to red when exposed to air.
[0034] M.p.: 164-168° C. TLC (EtOAc/hexane, 1:2). R f =0.34. 1 H NMR (CDC1 3 , 300 MHz): δ1.87 (4 H, m), 2.51 (4 H, m), 2.94 (4 H, m), 5.63 (1 H, s). 13 C NMR (CDCl3/CD 3 OD, 100 MHz): δ20.6 (2 x), 21.9 (2 x), 50.1 (2 x), 91.4, 100.8 (2 x), 144.6, 152.3(2x). IR(KBr):2932,2846, 1593,1434,1288,1142, 1089cm −1 . MS(FAB):m/z 205 (M + ).
Embodiment 12: Synthesis of 8. 10-Dibenzoyloxyjulolidine and 8.1 O-Dihydroxyjulolidine
[0035] A mixture of 3,5-(dibenzoyloxy)aniline(3.5 g, 11.3 mmol), 1-bromo-3-chloropropane (12.7 g, 9.2 ml, 84.5 mmol), triethylamine (3.5 g, 4.7 ml, 33.3 mmol) and dioxane(45 ml) was heated and refluxed at 96-100° C. for 24 hours. Volatiles were removed and the resulting product was extracted with CH 2 Cl 2 (30 ml) and rinsed by a saturated NaHCO 3 aqueous water solution (15 ml). The resulting aqueous phase was extracted with CH 2 Cl 2 (15 ml×2). The CH 2 Cl 2 extracts were combined, concentrated, and added ethyl acetate to force sedimentation. The sediments were removed by filtration. The remaining filtrate solution was concentrated and subjected to silica gel column chromatography by elution with EtOAc/hexane.
[0036] The resulting product is recrystallized from EtOAc/hexane to give light yellow crystals of 8,10-dibenzoyloxyjulolidine (1.2 g, 3.1 mmol) in 28% yield.
[0037] M.p. 84-86° C. TLC (EtOAc/hexane, 1:9). R f =0.44. 1 H NMR (CDCl 3 , 300 MHz): δ1.90-1.98 (4 H, quint, J=6 Hz), 2.70 (4 H, t, J=6 Hz), 3.06 (4 H, t, J=6 Hz), 4.99 (4 H, s), 5.98 (1 H, s), 7.20-7.41(10 H, m). 13 C NMR (CDCl 3 , 100 MHz): δ21.13 (2 x), 21.91 (2 x), 50.14 (2 x), 70.04 (2 x), 87.45, 103.71 (2 x), 127.08 (4 x), 127.50 (2 x), 128.45 (4 x), 137.87 (2 x), 144.56, 154.98 (2 x). IR(KBr): 2919,2853,1600, 1493, 1454,1281, 1169cm −1 . MS: m/z385(M + ),294(M−Bn + ),91 (Bn + ).
[0038] In a solution of 8,10-dibenzoyloxyjulolidine (1.2 g, 3.1 mmol) in ethyl acetate (60 ml), a 10% palladium catalyst on charcoal support is added. The solution is covered by hydrogen balloon and stirred for 6 hours. The solution is filtered, concentrated and subjected to silica gel column chromatography to give 520 mg of 8, 10-dihydroxyjulolidine in 81% yield.
EXAMPLE 13
Synthesis of 8, 10 -Dihydroxy-9-Formyljulolidine and the Subsequent Condensation with Diethyl Malonate
[0039] [0039]
[0040] A mixture of 8,10-dihydroxyjulolidine (1.00 g, 5 mmol), N,N-dimethylformamide (1 ml) and a mixture of phosphoryl chloride (POCl 3 , 790 mg, 0.5 ml, 5.6 mmol) in N,N-dimethylformamide (5 ml) was stirred at room temperature for 1 hour. Water (1 ml) was added, the resulting precipitates were filtered, and the filtrate was concentrated to give 8,10-dihydroxy-9-formyljulolidine (formula 3 above, 932 mg) in 80% yield. 1 HNMR (CDCl 3 , 200 MHz)” δ1.82 (4 H, m), 2.47 (4 H, m), 3.16 (4 H, m), 9.70 (1 H, s).
[0041] A mixture of 8,1 0-dihydroxy-9-formyljulolidine (232 mg, 0.9 mmol), diethyl malonate (114 mg, 0.1 ml, 1 mmol) and piperidine (172 mg, 0.2 ml, 2 mmol) in acetonitrile (CH 3 CN, 1 ml) and benzene (3 ml) was heated and refluxed for 2 hours. The solvents were removed under reduced pressure, and the crude product was purified by recrystallization with ethyl acetate to give the coumarin compound (formula 4 above, 293 mg) in 89% yield. 1 H NMR (CDCl 3 , 300 MHz): δ1.36 (3 H ,t, J=6.0 Hz), 1.93 (4 H, m), 2.61 (2 H, t, J=6.4 Hz), 2.77 (2 H, t,J=6.4 Hz), 3.28 (4 H, m), 4.33 (2 H, q, J=6.0 Hz), 8.75 (1 H, s).
EXAMPLE 14. CONDENSATION OF 8. 1 O-DIHYDROXYJULOLIDINE AND ETHYL ACETOACETATE
[0042] [0042]
[0043] A mixture of 8,10-dihydroxyjulolidine (208 mg, 1 mmol), ethyl acetoacetate (220 mg, 16 mmol), zinc chloride (ZnCl 2 , 12 mg, 1.2 mmol) and ethanol(10 ml) was heated and refluxed for 22 hours. The solvents were removed under reduced pressure, and the crude product was purified by recrystallization with ethyl acetate to give the coumarin compound(formula 5 above, 225 mg) in 83% yield. 1 H NMR (CDCl 3 , 200 MHz): δ1.90 (4 H, m), 2.49 (3 H, s), 2.53 (4 H, m),3.23 (4 H, m), 5.67(1 H, s).
EXAMPLE 15. SYNTHESIS OF THE 4-CYANO SUBSTITUTED COUMARIN
[0044] [0044]
[0045] A suspension of a coumarin of (formula 5 as shown in Embodiment 13, 520 mg, 1.66 mmol) in N,N-dimethylformamide (10 ml) was added a 30% sodium cyanide (163 mg, 3.32 mmol) aqueous solution(0.4 ml) at room temperature. The mixture was stirred and cooled in an ice bath. Bromine (292 mg, 1.83 mmol) was added dropwise with care. The mixture turned from orange color to pink color, and precipitates were formed. The mixture was stirred at room temperature for 16 hours. The precipitates were filtered and rinsed with small amounts of N,N-dimethylformamide and water. The filtrate was extracted with ethyl acetate (60 ml×3). The extract was concentrated and the remaining crude product was purified by recrystallization to give the coumarin compound (formula 6 above, 540 mg) in 96% yield.
[0046] M.p. 175-177° C. TLC(EtOAc/hexane, 1:1). R f =0.24. 1 HNMR(CDCl 3 ,200 MHz): δ1.39 (3 H, t, J=7 Hz), 1.94-1.96 (4 H, m), 2.74-2.84 (4 H, m), 3.31-3.39 (4 H, m), 4.40 (2 H, q, J=7 Hz), 7.24 (1 H, s). 13 CNMR (CDCl 3 , 50 M): δ14.0, 19.9, 20.9, 27.4,50.0,50;4,62.2,106.0,106.5,110.2, 113.2,120.7,124.8,127.4, 149.2, 152.0,157.0, 162.7. IR (KBr): 2335, 1748, 1614 cm −1 . MS: m/z 338 (M + ), 310 (M + —CO), 266 (M + —CO 2 C 2 H 5 ), 57 (C 3 H 7 N + ). UV-vis: λ max =508.8 nm (ε=27478) in EtOH; 503.6 nm (ε=31236) in acetone; 494.4 nm (ε=21726) in THF. Fluorescence: λ max =560 nm in EtOAc; 559 nm in THF; 569 nm in acetone; 575 nm in EtOH. Anal. calcd for C 19 H 18 N 2 O 4 : C, 67.44; H. 5.36; N, 8.27. Found: C, 67.15; H, 5.36; N, 8.17.
[0047] As the present invention has been shown and described with reference to preferred embodiments thereof, those skilled in the art will recognize that the above and other changes may be made therein without departing form the spirit and scope of the invention.
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The present invention relates to 8-hydroxyjulolidine, its analogous compounds and their preparation methods. The invented method comprises one single step of cyclization reactions of 3-aminophenol or 1,3-dihydroxyaniline with 1,3-dihalopropane or its analogs, to prepare the desired julolidines with improved yields. The products of this invention have the following structures:
wherein R 1 and R 2 represent independently H, halogen, hydroxyl or alkyl. The method of this invention includes the following chemical reaction:
wherein X and Y represent independently halogen, acyloxyl, sulfonyloxyl or phosphoryloxyl and R 1 and R 2 are as defined above.
This invention also discloses method for the preparation of various coumarins by additionally reacting the produced 8-hydroxyjulolidine and its analogs with appropriate reagents such as malonate and acetoacetate. This invention also discloses the products and intermediates prepared therefrom.
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[0001] The present application claims priority from PCT Patent Application No. PCT/EP2013/001956 filed on Jul. 3, 2013, which claims priority from German Patent Application No. DE 10 2012 013 346.4 filed on Jul. 6, 2012, the disclosures of which are incorporated herein by reference in their entirety.
1. FIELD OF THE INVENTION
[0002] The present invention is directed to a heating block for heating a liquid medium, particularly for heating water. The present invention is further directed to a continuous-flow heater with a heating block.
[0003] It is noted that citation or identification of any document in this application is not an admission that such document is available as prior art to the present invention.
[0004] A heating block for heating water such as is used, for example, in an electric continuous-flow heater, is well known. A heating block of this type is basically constructed to guide water to be heated into a cavity such as meanderingly arranged heating conduits. Heating wires carrying electric current for heating the water are arranged in these heating conduits and therefore, as intended, in the water. This electric current can be controlled, e.g., by a semiconductor switch such as a triac. Correspondingly, the triac is to be electrically connected to the heating wire so that the current can flow from the triac to the heating wire. Further, the triac must be supplied in turn with electric current and also triggered correspondingly in order to control the electric current through the heating wire as needed.
[0005] In this regard, the connection and triggering of the semiconductor switch is particularly problematic. On the one hand, a control switch is provided on a corresponding control board, possibly with a microprocessor. The control, per se, requires relatively small currents and voltages. On the other hand, the semiconductor switch generates high currents which are fed into the heating wire and, in bare wire systems, make direct contact with the water to be heated. The semiconductor switch must form a kind of link therebetween and take into account the very different conditions with respect to connecting and controlling. In addition, the high current which leads to a required heating in the heating wire heats the semiconductor switch in an unwanted manner. The semiconductor switch must be cooled in a corresponding manner as the case may be.
[0006] It has already been suggested for this purpose in German Patent Application DE 102 09 905 A1 to arrange the semiconductor switch directly on a closure piece instead of on a board, this closure piece in turn being in direct contact with the water to be heated. In this way, the semiconductor switch is cooled by the water via the closure piece. This step which suggests relocating the semiconductor switch from a board to the closure piece is also intended to reduce the cost of contacting for the semiconductor switch and therefore for the device as a whole.
[0007] However, it is still expensive to connect semiconductor switches even with a solution of this type.
[0008] It is noted that in this disclosure and particularly in the claims and/or paragraphs, terms such as “comprises”, “comprised”, “comprising” and the like can have the meaning attributed to it in U.S. patent law; e.g., they can mean “includes”, “included”, “including”, and the like; and that terms such as “consisting essentially of” and “consists essentially of” have the meaning ascribed to them in U.S. patent law, e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the invention.
[0009] It is further noted that the invention does not intend to encompass within the scope of the invention any previously disclosed product, process of making the product or method of using the product, which meets the written description and enablement requirements of the USPTO (35 U.S.C. 112), such that applicant(s) reserve the right to disclaim, and hereby disclose a disclaimer of, any previously described product, method of making the product, or process of using the product.
SUMMARY OF THE INVENTION
[0010] Therefore, it is the object of the present invention to address at least one of the problems mentioned above. In particular, a heating block is to be improved in such a way that a semiconductor switch for controlling a heating current can be installed and connected in the simplest possible manner and as permanently as possible. At the least, an alternative solution is to be found.
[0011] A heating block of this kind is provided for heating a liquid medium, particularly water. It comprises a heating block with a cavity for receiving or guiding the medium. In particular, a heating block of this type is intended for a continuous-flow heater and, in this case, the heating block body guides the medium, namely particularly water, while it is heated. However, fundamentally different variants can also be considered in which a liquid medium such as, e.g., water is heated in a reservoir or the like.
[0012] At least one electric heating element for heating the medium is arranged in the cavity. The electric heating element is energized for this purpose by an electric current which results in heating of the heating element. A heating element of this kind is formed particularly as a heating wire, particularly as a so-called bare heating wire, in direct galvanic contact with the liquid medium, namely particularly water.
[0013] Further, a semiconductor switch is provided, particularly a triac. The current which is to flow through the heating element is controlled by this semiconductor switch in order thereby to control the heating power of the heating element. Usually, this semiconductor switch provides the current in a pulsed manner. The average amount of current or current strength can possibly be influenced by changing the pulse pattern. Of course, the semiconductor switch can also switch off the current completely when heating is not to be carried out.
[0014] Further, a closure piece is provided for closing an opening in the heating block body to the cavity. An opening of this kind accordingly forms an access to the cavity, and the heating element can also be inserted into the cavity through this opening. If a plurality of heating elements are provided, a corresponding quantity of openings and closure pieces can also be provided.
[0015] The semiconductor switch is electrically and thermally conductively connected to the closure piece by a first connection terminal such that an electrical connection of the first connection terminal to the heating element is carried out via the closure piece and a thermal connection of the first connection terminal to the medium is carried out via the closure piece.
[0016] Further, the semiconductor switch is directly connected to a control board by a second connection terminal so that the semiconductor switch is also spatially arranged and mechanically connected directly between the control board and the connection piece.
[0017] Accordingly, on the one hand, the semiconductor switch sits on the closure piece so that an electric and thermal connection can be directly produced basically without supplementary elements. Further, the semiconductor switch sits directly on the printed circuit board so that additional connection lines, particularly connection wires or connection slots, between the printed circuit board and semiconductor switch can also be dispensed with at that location. Accordingly, in particular, a heating block is suggested in which these elements, namely particularly the printed circuit board, the semiconductor switch, the closure piece and preferably also the heating block body, can be adapted to one another for this purpose. This not only simplifies the connection possibility, but the elements are also thermally coupled to one another and closely cooperate to this extent. The board and/or heating block body can be adapted to one another for this purpose.
[0018] The control board is preferably mechanically connected to the closure piece via the semiconductor switch, particularly such that the three elements, i.e., the control board, semiconductor switch and closure piece, form an assembled total component part. For example, the semiconductor switch can be fixedly connected to the board inter alia by soldering. Further, the semiconductor switch can be fixedly connected to the closure piece inter alia by screwing. Preferably, a galvanic connection takes place by carrying out a mechanical connection. For example, the semiconductor switch with the first connection terminal is fixedly screwed to the closure piece in a conductive location such that a galvanic connection is produced between the first connection terminal and the closure piece.
[0019] It is advantageous when the control board, or at least a portion of the control board, is connected to the closure piece and the semiconductor switch arranged between these two elements such that a sandwich structure results in which the semiconductor switch correspondingly forms a middle layer, or the middle layer, of this sandwich structure. This results in a snug connection of the control board, semiconductor switch and closure piece which is advantageous in mechanical, electrical and thermal respects. The semiconductor switch can be supplied via the control board with the required energy, namely with the required supply current, and it can be triggered via the control board by control signals, namely switching signals. In this case, there is no need for a conducting wire, cord or the like for either the supply current or the control signals for connecting the semiconductor switch.
[0020] At the same time, the semiconductor switch is wirelessly connected to the closure piece and, via the latter, to the heating element. Correspondingly, no cable, line, cord or the like is required either on the input side or output side for connecting the semiconductor switch.
[0021] The closure piece is preferably in electrical contact with the medium insofar as this liquid medium flows through or fills the hollow body as is intended. Accordingly, there is a galvanic connection between the closure body and the liquid medium, particularly water, and therefore, as a result, there is also a galvanic connection between the first connection terminal of the semiconductor switch and the liquid medium. The heating block, particularly the semiconductor switch, is correspondingly configured for this type of use with a direct galvanic contact with the liquid medium to be heated. Correspondingly, electric insulation paths are also provided in the heating block. For this purpose, the heating block body is preferably fashioned from a nonconductive material, e.g., nonconductive plastic, in other respects, that is, with the exception of the closure piece or the plurality of closure pieces and further possible minor exceptions. In case of a continuous-flow heater, portions of insulation ducts can be provided which can achieve sufficient insulation along corresponding sections of conduit, also through the water.
[0022] A high thermal conductivity is also achieved by means of this direct electrical contact. In every case, there is a close relationship between electrical conductivity and thermal conductivity in many metal conductors.
[0023] According to an embodiment, it is suggested that the heating block is characterized in that a heating coil fastening pin is provided for the electrical connection of the semiconductor switch to the heating element, wherein the heating coil fastening pin is provided for producing a thermal connection between the semiconductor switch and the medium so that the semiconductor switch is cooled through the medium via the heating coil fastening pin.
[0024] Accordingly, in particular, a heating coil fastening pin extends into the medium or into the cavity. A bore hole, for example, to which the heating element, e.g., in the form of a heating wire, is mechanically, electrically and partially also thermally connected may be provided in this area of the heating coil fastening pin extending into the medium or cavity. Further, the heating coil fastening pin has a corresponding contact surface by which it comes in contact with the liquid medium. Aside from a galvanic connection to the medium via this contact surface, the latter also realized a thermal connection. The farther the pin projects into the medium and the larger the surface of this pin in this region, the better the emission of heat from the heating coil fastening pin to the medium. In this way, by means of the direct connection of the semiconductor switch to the connection piece and, therefore, to the heating coil fastening pin, heat from the semiconductor switch can be given off via the closure piece and further via the heating coil fastening pin into the medium.
[0025] It is advantageous to provide the heating coil fastening pin in such a way that it is integrated in the closure piece, particularly in such a way that the heating coil fastening pin forms an individual element of one piece, particularly a metal piece, with the closure piece or with the rest of the closure piece, except for a seal, usually made of rubber, insofar as this seal is part of the closure piece and not part of the opening of the heating block body. Accordingly, the closure piece can be formed in a simple manner with heating coil fastening pins and, therefore, overall with a connection possibility for the heating element. An additional electrical connection of the heating coil fastening pin and closure piece is accordingly dispensed with and any possible problems with bad connections are therefore obviated.
[0026] Further or alternatively, it may be advantageous that the heating coil fastening pin has connection means at its side facing the medium for electrical connection of the heating element. Connection means of this type can be a bore hole in a simple case.
[0027] Further or alternatively, it is advantageous when the heating coil fastening pin and/or the closure piece has at a side remote of the medium a receptacle for receiving fastening means for fastening the semiconductor switch to it. These fastening means can be, for example, a threaded bore hole into which a screw is screwed for fastening the semiconductor switch, particularly for screwing down a first connection terminal of the semiconductor switch. For this purpose an embodiment of a heating coil fastening pin can be used in which the heating coil fastening pin projects into the medium or into the hollow body and in so doing has an outer diameter that is greater than the screw such that the screw can be screwed into this heating coil fastening pin from the inner side. Accordingly, the length of the screw can be greater than the thickness of the closure piece so as to prevent excessively high thermal resistance of the closure piece and, therefore, inadequate cooling of the semiconductor switch via the closure piece toward the medium.
[0028] The closure piece is preferably provided for inserting into the opening of the heating block body from the inner side proceeding from the cavity of the heating block body. To this end, the closure piece has an outer rim by which it can be fitted to or placed at the corresponding opening from the inner side. This outer rim is accordingly placed against a corresponding circumferential rim of the opening, namely, proceeding from the side of the cavity. Also, the outer rim is accordingly provided as circumferential rim. Accordingly, its outer circumference exceeds a circumference of the opening and, in case of a circular shape of closure piece and opening, the outer diameter of this circumferential outer rim is correspondingly greater than the inner diameter of the opening. The closure piece is accordingly inserted into the opening from the inner side and its outer rim lies on a corresponding wall in which the opening is formed. During operation of the heating block, i.e., when a liquid medium such as water flows through the heating block, the closure piece can be pressed even farther into the opening by a corresponding overpressure in the heating block body and in so doing possibly further improves the sealing, particularly can lead to a re-sealing.
[0029] The semiconductor switch, namely particularly the triac, can be fastened to the closure piece after the latter has been inserted into the opening. In particular, the closure piece can be inserted into a shell or partial shell of the heating block body from the inner side in such a way that the heating block body can then be composed of this shell or partial shell and a further shell or further partial shells so as also to form the cavity in its entirety. In particular, the shells or partial shells can be welded. Subsequently, when the heating block body is finished to this extent, the semiconductor switch, particularly the triac, can be fastened, particularly by screwing, from the outer side. Accordingly, an advantageous solution is found particularly for the use of a triac in which the closure piece is inserted into the opening from the inner side and the triac can be fastened subsequently.
[0030] Accordingly, as has been described, it is advantageous when the heating coil fastening pin and the closure piece are substantially formed as a one-piece metal body. It is likewise advantageous when the receptacle for receiving fastening means is formed as a blind hole with internal thread in order to screw in fastening means with external thread, particularly a metal screw.
[0031] The invention and the above-mentioned embodiment forms have been described substantially with reference to a heating element and a closure piece and correspondingly a semiconductor switch. In an advantageous manner, a plurality of heating elements, for example, three heating elements, and correspondingly three closure pieces and correspondingly three semiconductor switches are provided.
[0032] In this case, the semiconductor switches can be accommodated on a control board, or all three—or two or more than three—semiconductor switches can advantageously be accommodated on an individual control board. Particularly in this case, the control board is adapted to the shape and configuration of the heating block body so that semiconductor switches which are correctly installed on the control board are seated directly at the required place in their respective closure piece when the control board is mounted on the heating block body. A connection to the respective closure piece can then be carried out, for example, simply via a mechanical connection, particularly simply by screwing to the closure piece by means of a screw.
[0033] In case three heating elements are used, they can be actuated in the manner of a 3-phase system and wired via a common star point. In the example in which a heating wire is used as heating element, this heating wire is accordingly electrically connected with one side at the star point and with the other side at the semiconductor switch.
[0034] The heating block is advantageously used in a continuous-flow heater according to one of the embodiment forms.
[0035] Further, a heating apparatus according to claim 9 is suggested, namely a heating apparatus such as one of the heating blocks which are described or claimed, only without heating block bodies.
BRIEF DESCRIPTION OF THE DRAWINGS
[0036] FIG. 1 shows a semiconductor switch between a board and a closure piece and part of a heating element schematically in a side sectional view;
[0037] FIG. 2 schematically shows a detail of a heating block body in a perspective view of two closure pieces;
[0038] FIG. 3 shows a semiconductor switch with a closure piece in a perspective view;
[0039] FIG. 4 shows the semiconductor switch with closure piece from FIG. 3 in a side view;
[0040] FIG. 5 shows the semiconductor switch with closure piece from FIGS. 3 and 4 in a front view;
[0041] FIG. 6 shows the semiconductor switch with closure piece from FIGS. 3 to 5 in a top view.
DETAILED DESCRIPTION OF EMBODIMENTS
[0042] It is to be understood that the figures and descriptions of the present invention have been simplified to illustrate elements that are relevant for a clear understanding of the present invention, while eliminating, for purposes of clarity, many other elements which are conventional in this art. Those of ordinary skill in the art will recognize that other elements are desirable for implementing the present invention. However, because such elements are well known in the art, and because they do not facilitate a better understanding of the present invention, a discussion of such elements is not provided herein.
[0043] The present invention will now be described in detail on the basis of exemplary embodiments.
[0044] FIG. 1 shows a sandwich structure in which a semiconductor switch 2 is arranged between a control board 4 and a closure piece 6 . The semiconductor switch 2 lies flat against an upper contact surface 8 at the control board 4 . The semiconductor switch 2 lies flat against a lower contact surface 10 at the closure piece 6 .
[0045] The control board 4 can accordingly provide the semiconductor switch 2 fastened thereto. For purposes of contacting, the semiconductor switch 2 has a plurality of connections 12 , namely three connections 12 , only one of which is shown because of the side view. A possible contacting of the connections 12 is shown schematically in FIG. 1 , and the connections 12 accordingly pass at an angle directly into a board connection area 14 on the control board 4 . The connection can also be carried out differently; a direct contacting of the connections 12 on the control board 4 is advantageous. Only a detail of the control board 4 is shown in FIG. 1 .
[0046] The closure piece 6 has a sealing ring 16 . Therefore, the closure piece 6 can be sealingly inserted into an opening. In so doing, the portions shown above the sealing ring 16 , particularly the lower contact surface 10 and, along with it, the semiconductor switch 2 , are outside of the heating block body into whose opening the closure piece 16 is inserted from the inner side, the closure piece 6 being inserted into the opening outward from the heating block body. An outer rim 50 is provided by which the closure piece 16 contacts a rim of the opening of the heating block body from the inner side. The rest of the elements are positioned substantially facing toward the cavity of the heating block body. In particular, the heating element 18 which is formed as heating wire and which is shown only partially and only schematically is located as intended in the medium to be heated, particularly in the water to be heated. The heating element 18 is fastened to and electrically connected with a connection wire portion 20 in a heating coil fastening pin 22 . The fastening is carried out in connection means 24 which are formed approximately like a bore hole 24 .
[0047] The above-mentioned heating coil fastening pin 22 is actually a portion of the closure piece 6 . This heating coil fastening pin 22 projects far into the medium in every case when used as intended. In this respect, the liquid medium also extends up to an inner surface 26 of the closure piece 6 which is basically provided adjacent to the lower contact surface 10 . Accordingly, there is merely a relatively thin cover layer 28 between the lower contact surface 10 and the inner surface 26 . Accordingly, heat from the semiconductor switch 2 can be given off via the cover layer 18 over a fundamentally large surface area to the liquid medium to be heated, particularly water. The lower contact surface 10 between semiconductor switch 2 and closure piece 6 and the inner surface 26 between cover layer 28 and liquid medium offer only a low thermal resistance insofar as this is noteworthy at all.
[0048] A fastening of the semiconductor switch 2 is carried out via a fastening tab 30 having a fastening opening 32 . A fastening screw 34 is snugly guided through the fastening opening 32 and screwed into a blind hole 36 having internal thread 38 . The blind hole 36 reaches far into the heating coil fastening pin 22 . In this way, a stronger and more secure connection can be produced between semiconductor switch 2 and closure piece 6 . An electric heating current for heating the heating element 18 can also flow via this connection. To this extent, the fastening tab 30 also forms a first connection terminal 30 of the semiconductor switch 2 .
[0049] Further the fixed mechanical connection by means of the fastening screw 34 which also produces an electrical connection is suitable for transmitting heat. Accordingly, heat can flow additionally to the indicated path directly via the cover layer 28 and also via the heating coil fastening pin 22 into the medium which is to be heated.
[0050] FIG. 1 shows a sandwich-type structure of—from top to bottom—control board 4 , semiconductor switch 2 and closure piece 6 . This sandwich-type structure allows a simple connection of the semiconductor switch to the heating element 18 as well as to the control board 4 . The entire construction which is achieved is relatively simple and in particular is formed directly and prevents unnecessary connection elements, particularly unnecessary wiring.
[0051] FIG. 2 shows a detail of a heating block body 200 with two closure pieces 206 inserted into corresponding openings. Located in the heating block body 200 below each closure piece 206 is a heating conduit 240 shown only by an outward curvature in the heating block body 200 . A heating element 18 which is connected to the respective closure piece 206 is inserted in each of these heating conduits.
[0052] Each of the two closure pieces 206 has a blind hole 236 with an internal thread so that a semiconductor switch can be placed on the closure piece 206 and screwed into this blind hole 236 . A common board, i.e., a collective board for the heating block body 200 , having the plurality of semiconductor switches can be provided for both closure pieces 206 and any further closure piece. The semiconductor switches can be arranged at the board in such a way that when the board is mounted at the heating block body 200 in an intended position a semiconductor switch is seated at a closure piece 206 , particularly in such a way that the semiconductor switch can be screwed to the respective blind hole 236 . The positioning means 242 shown in FIG. 2 , which can also be referred to and formed as positioning projections or positioning pins, can be used to position a control board of this type. The heating block body 200 can be formed of two injection molded parts, for example, namely particularly an upper partial shell and a lower partial shell. FIG. 2 correspondingly shows an upper heating block body partial shell 244 which is fabricated as injection molded parts, and the positioning means 242 are formed in the injection mold and, correspondingly, integrally in this upper partial shell 244 . Accordingly, when a control board is neatly positioned by these positioning means 242 , the semiconductor switches fastened thereto are also correctly placed at the position for connecting to the respective closure piece 206 .
[0053] FIGS. 3 to 6 show four different views of a semiconductor switch 102 which is fastened to a closure piece 306 by means of a fastening screw 343 . Depending upon the view, it can be seen that the semiconductor switch 302 sits directly on a cover layer 328 with a fastening tab 330 . To this end, the fastening screw 334 is screwed through the fastening tab 330 into a blind hole of the closure piece 306 . The fastening screw 334 is approximately aligned with a heating coil fastening pin 322 . The heating coil fastening pin 322 has a bore hole 324 as connection means for connecting a heating element, particularly a heating wire.
[0054] A sealing ring 316 is provided for sealing the inserts. Further, the semiconductor switch 302 has three connections 312 which can be used for actuating and for supplying with supply current.
[0055] Therefore, a solution is proposed which does away with the previous cooling zones which were coupled directly with the control electronics. Cooling subassemblies of this kind were very cost-intensive and also necessitated costly devices for handling in electronics manufacture. A solution is now suggested in which semiconductor switches, particularly triacs, namely triacs such as semiconductor switch 2 in FIG. 1 or semiconductor switch 302 in FIGS. 3 to 6 , can be connected in a more economical way than heretofore.
[0056] In the suggested solution, cooling surfaces such as the lower contact surface 10 in FIG. 1 inter alia are also coupled with heating coil fastening pins such as heating coil fastening pins 22 and 322 . This coupling also advantageously includes the use of fastening screws 34 according to FIG. 1 and fastening screws 344 from FIGS. 3 to 6 which achieve a direct fastening of the semiconductor switches or triacs and which also produces a good thermal connection with potential for cooling. A thermal connection is also formed via the fastening screws 34 and 334 .
[0057] In this case, the semiconductor switches or triacs contact the heating coil fastening pin and also the fastening screw in the manner of an electrically conductive unit so that additional connections, particularly connection cables or cords from the triac to the heating body pin and fastening screw, are dispensed with.
[0058] Accordingly, it is suggested that the triacs be constructed as non-insulated component parts. The triacs are arranged on the electronics board or control board in such a way that, when assembled, they are seated directly over the heating conduits, e.g., heating conduits 240 . In so doing, the heating body pins are spatially arranged in such a way that they lie directly below the triacs.
[0059] While this invention has been described in conjunction with the specific embodiments outlined above, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, the preferred embodiments of the invention as set forth above are intended to be illustrative, not limiting. Various changes may be made without departing from the spirit and scope of the inventions as defined in the following claims.
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A heating block including a heating block body which receives/guides a liquid medium, an electric heating element arranged in the cavity for heating the medium via electric current, a semiconductor switch for controlling the electric current flowing through the heating element to control a heating power of the heating element, and a closure piece for closing an opening in the heating block body to the cavity element. The semiconductor switch is electrically and thermally conductively connected to the closure piece via first connection terminal to electrically connect the first connection terminal to the heating element via the closure piece, and to thermally connect the first connection terminal to the medium via the closure piece. The semiconductor switch is directly connected to a control board by a second connection terminal so that the semiconductor switch is spatially arranged and mechanically connected directly between the control board and the connection piece.
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BACKGROUND OF THE INVENTION
The present invention relates to 8-methyl-non-2ynol the corresponding aldehyde, esters of organic acids and the alcohol in which the carbonyl is not conjugated with a double bond or aromatic ring and acetals of the aldehyde found useful in the area of flavor alteration whether by enhancement of flavor characteristics in a substance, modification of flavor or by complete or partial masking of flavor. Still more particularly, the invention relates to incorporation of woody flavor compounds selected from the group consisting of 8-methyl-non-2-ynol, esters of 8-methyl-non-2ynol and lower alkyl organic acids such as formic, acetic, etc. in which the carbonyl is not conjugated with a double bond or aromatic ring, 8-methyl-non-2ynal and its acetals and mixtures thereof in coffee to reduce the caramel, acid, and sour flavor of coffee; modify and improve the green, earthy, and buttery notes of coffee; and add a desirable woody, regular coffee flavor to the foodstuff. The compounds employed have particular application to soluble and regular coffee which may be deficient in a woody flavor.
DESCRIPTION OF THE PRIOR ART
In the field of flavor enhancement, it has been general practice to employ synthetic and naturally isolated compounds and compositions to enhance or mask the flavor of foodstuffs. Generally, isolation of single flavors does not allow one to predict equivalent flavors since compounds of greatly differing structure have been found to produce approximately the same flavor character while compounds of similar structure frequently differ appreciably in taste. Consequently, the identification of desirable flavor components requires synthesis and trial of individual candidates until compounds are identified which have desirable flavors.
For many years, coffee technologists have searched for flavor enhancing compounds which would produce the flavor note generally described by coffee experts as "woody." Recently, a number of woody flavored 2-nonenals and 2-nonenols have been identified in U.S. Pat. No. 3,655,397, to have this character. In the course of investigating those compounds and others, we have discovered the compounds employed in the composition and process of this invention.
SUMMARY OF THE INVENTION
The general purpose of this invention is to provide compounds and compositions containing compounds which will enhance coffee flavored foodstuffs by imparting to them a regular coffee flavor characterized by experts as woody.
The flavor enhancement is achieved by the addition of a small but effective amount of woody flavored compounds to the foodstuff to be flavored. The compounds, singly or mixtures, produce a coffee flavor when added in minute amount, generally in parts per billion, to water or foodstuffs.
It is an object of this invention to provide compounds for the flavor alteration of foodstuffs, particularly coffee deficient in woody flavor.
It is a further object of this invention to describe processes for employing woody compounds in concentrates useful for enhancing the flavor of foodstuffs, particularly coffee.
DESCRIPTION OF THE INVENTION
The compounds employed are characterized by the following formulas: ##STR1## esters of organic acids and the preceding compound I; ##STR2## where R1, is hydrogen or lower alkyl or substitute lower alkyl, 8-methyl-non-2ynal; ##STR3## acetals of 8-methyl-non-2ynal; Where R is lower alkyl or substituted lower alkyl.
Prop-1-ynol was added to dihydropyran in the presence of hydrochloric acid to give prop-1-ynyltetrahydropyranyl ether. The ether was alkylated with 5-methylhexyl bromide. The resultant product was hydrolyzed with sulfuric acid to the desired alcohol, 8-methylnon-2yn-1-ol.
Oxidation of 8-methylnon-2yn-1-ol with manganese dioxide in refluxing ether gave 8-methylnon-2yn-1-al. The aldehyde was converted to acetals using appropriate acidic catalysts.
Representative of the woody compound of this invention are 8-methyl-non-2yn-1-ol, 8-methyl-non-2yn-1-al, 8-methyl-non-2yne dimethylacetal, 8-methyl-non-2yne diethyl acetal, 8-methyl-non-2ynyl acetate, 8-methyl-non-2ynyl isobutylate, 8-methyl-non-2ynyl phenylacetate and the like.
The compounds for Formulas I, II, III and IV are useful for enhancing the flavor of food. The compounds are particularly useful to enhance coffee flavored foodstuffs where a regular coffee flavor generally characterized by coffee experts as woody is desired but deficient--such as regular coffees like Robustas, decaffeinated coffee, soluble coffee; and coffee flavored foods such as icings, drinks, Postum brand beverage, desserts, candies, and the like.
The compounds of Formulas I-IV and mixtures thereof give coffee flavor when added to water or foodstuffs. In addition to imparting to coffee a regular, coffee-like flavor having a strong woody note, these compounds exert a balancing effect on other desirable coffee notes such as the green, earthy, and buttery flavors while masking the undesirable acid, sour, and caramel flavors. The compounds also exert a blending effect of the overall brew flavor of soluble coffee. The compounds of Formulas I-IV may be added to any coffee including soluble coffee, decaffeinated coffee either regular or soluble and regular roasted and ground coffee. The compounds of Formulas I to IV may also be incorporated with other coffee flavor fractions, both synthetic and those obtained from coffee, and with these flavors exert a balancing effect while strengthening the woody regular coffee flavor.
Depending on the flavor desired, the compounds of Formulas I to IV can be incorporated in the foodstuff either alone, combined with other flavor ingredients, or with carriers. In flavoring soluble coffee, the woody compounds may be either added to regular coffee prior to extraction, to coffee percolate prior to drying, or may be plated on or mixed with the dried coffee. Since only a minute amount of the flavor and aroma compounds are needed, it is preferred to incorporate them in an edible carrier or concentrate prior to addition to the coffee. The concentrate or carrier may be liquid, syrup, or solid, depending on its ultimate use. For example, the compounds of Formulas I to IV may be incorporated in ethanol, propylene glycol; oils such as cottonseed, coffee, peanut or the like; or other edible vehicles to form a concentrate for convenient shipping, storage, and addition to the foodstuff. For example, oil containing a compound of Formulas I to IV or mixtures thereof may be plated on soluble coffee to enhance its flavor or alternatively, an oil containing the flavor compound may be incorporated in extract and dried. Dry concentrates containing the compounds of Formulas I to IV or mixtures thereof may also be prepared by employing film-forming compositions such as gums--like gum arabic, pectins, alginates, and the like; starch breakdown products such as Capsul (National Starch), Morex 1918 (Corn Products), Maltrin 10 (Grain Processing), and the like; candy melt systems and other art-recognized stabilizing or diluent systems. In forming any concentrate, the proportions of the compounds of Formulas I to IV therein is not critical provided the level of flavoring is controlled to give an enhanced coffee flavor and an even distribution of the flavor concentrate throughout the foodstuff to be flavored.
Minute amounts of the compounds of Formulas I to IV are sufficient to produce an enhancement of coffee flavor in foodstuffs. For example, in regular or soluble coffee beverages, say from about 1 to 1.5% coffee solids, the compounds can be employed to produce a change in cup flavor and aroma but a change which cannot be described as a particular flavor. Alternatively, proportions sufficient to be recognized as woody may be employed. The threshold flavor level for the compounds of this invention is about 30ppm with a woody flavor evident at about 75ppm on a dry coffee solids basis.
The flavor impact of the compounds of Formulas I to IV and mixtures thereof is easily adjusted by varying the concentration of the flavoring compounds employed in the foodstuff. It is to be expected that adjustment will be necessary depending on the particular foodstuffs being flavored. Initial panel screening by those of ordinary skill in the art is used to determine the threshold and proper strength level for the particular foodstuff in which the flavor is employed.
The compounds of Formulas I to IV are particularly useful for balancing the natural flavor of spray dried and freeze-dried soluble coffee, decaffeinated coffee, both soluble and regular, and regular coffee of various blends or single varieties, particularly those having high Robusta content. The flavor compounds are particularly preferred for imparting a woody flavor to the preceding coffees deficient, partially or totally, in that flavor. However, even at levels below the woody threshold level, balancing of flavor is noted by expert tasters. The flavor compounds of Formulas I to IV are also particularly useful when combined with steam-generated natural coffee aromas or enhancers where there is produced a blending or smoothing of coffee aroma and flavor and a masking of the undesirable sourness and caramel characteristics often associated with coffee. Similar improvement is noted for mixtures of synthetic and natural coffee aromas and flavors. In addition to the application of the compounds of Formulas I and IV in foodstuffs, these flavoring agents may also be employed in edible substances such as pharmaceuticals, where a woody regular coffee note is desired.
The invention is now illustrated but not limited by the following examples:
EXAMPLE I
8-methylnon-2-yn-1-ol
168g. (3 mole) of prop-1-ynol were added with stirring to a mixture of 269g. (3.2 mole) of anhydrous dihydropyran and 0.5 ml of concentrate hydrochloric acid. The reaction is exothermic and the temperature is maintained at 60° C by external cooling when the addition is complete, the mixture is further maintained with stirring for 1 hour whereupon it is washed with dilute sodium carbonate. Distillation afforded 372g. (89%) of prop-1-ynltetrahydropyranyl ether, b.p. 65°-6° C/10mm.
70g. (0.5 mole) of prop-1-ynyltetrahydropyranyl ether in 200 ml of dimethyl sulfoxide were added with stirring to a solution of 11.5g. (0.5 mole) of lithium amide in 200 ml of dimethyl sulfoxide. Stirring was continued for 1 hour and 5-methylhexyl bromide 89g. (0.5 mole) were added over 45 min. External cooling was necessary to keep the temperature at 30° C. After 3 hours, the mixture was poured into 1 liter of ice-water. The mixture was extracted with petrol-ether, and the organic phase washed with 10% sulfuric acid, and then water. The solution was dryed over magnesium sulfate concentrated and distilled at 100°-103° C/0.01mm to give 82.6 (70%) of 8-methylnon-2-ynyl tetrahydropyranyl ether.
A mixture of 13g. (0.5 mole) of 8-methylnon-2-ynyltetrahydropyranyl ether and 250 ml of 10% sulfuric acid was heated at 90° C for 1/2 hour. Steam distillation gave 800 ml of distillate which, by extraction with petrol-ether, washing with water, drying over magnesium sulfate and concentrate gave on vacuum distillation 7.6g. (90%) of 8-methylnon-2-ynol, b.p. 67°-8° C/0.01mm.
NMR: 0.8 (3H,s), 0.92 (3H,s) 1.32 (7H,m), 2.16 (2h,m), 4.18 (2H,s) 4.33 (1H,s) δ ppm;
IR: 3320 and 2220 cm.sup. -1;
MS: m/e : 43 (100), 41 (87.5), 55 (76), 67 (53.6), 93 (38), 121 (8.4), 123 (7.8), 111 (4.7).
EXAMPLE II
8-Methylnon-2-yn-1-al
Five gms. (0.033 mole) of 8-methylnon-2-yn-1-al was added to a vigorously stirred mixture of 50 gms. (0.57 mole) of manganese dioxide in 500 ml of ether (cooled in ice water). After 1 hour the ice bath was removed and the mixture stirred for 5 hours. The manganese dioxide was filtered and the ether distilled. The residue was purified by vacuum distillation to give 8-methylnon-2-yn-1-al.
EXAMPLE III
1,1-dimethoxy-8-methylnon-2-yne
One gm. (0.007 mole) of 8-methylnon-2-yn-1-al, 10 gm. (0.1 mole) of trimethylorthoformate and 0.2 g of para-toluene-sulfuric acid were distilled. Methyl formate and methyl alcohol were collected. The solution was diluted with 15 ml of water and extracted with ether. The ether solution was washed with 5% sodium bicarbonate, and then water. The ether extract was dried over sodium sulfate, concentrate and distilled under vacuum to give 1,1-dimethoxy-8-methyl-non-2-yne.
EXAMPLE IV
2-(7-methyloct-2-yne) dioxolane
2 gm. (0.014 mole) of 8-methylnon-2-yn-1-al, 3 gm. (0.02 mole) triethylorthoformate, 2.5 gm. (0.04 mole) of ethylene glycol and 0.1 g of ammonium chloride were distilled. Ethyl formate and ethyl alcohol were collected. The solution was diluted with 20 ml. of water and extracted with ether. The ether extract was washed with 5% sodium bicarbonate and then water. The ether extract was dried over sodium sulfate contrate and distilled under vacuum to give 2-(7-methyloct-2-yne) dioxolane.
EXAMPLE V
Roasted coffee extract is prepared from roasted coffee by normal commercial techniques to obtain a percolate of 15-50% coffee soluble solids. Sufficient 8-methyl-non-2-ynol is added to give a woody, natural coffee flavor at 1.2% coffee solids in aqueous solution. The mixture is placed in cooled trays and frozen at a thickness of less than one-half inch. A frozen mixture of extract and aroma is then freeze dried in a commercial drying unit to produce a freeze-dried coffee having enhanced woody flavor.
Instead of freeze drying the enhanced percolate, it may be spray dried instead. If desired, a portion of the percolate may be employed to fix the flavor compound by any known drying procedure and then mixed with unenhanced dried soluble coffee.
EXAMPLE VI
To 8 ounces of boiling water is added 2.84g. Instant Maxwell House (IMH) brand soluble coffee to give a 1.2% solids solution. To this solution is added portions of a 1% by weight solution of 8-methyl-non-2ynol in ethanol until a threshold flavor level and flavor intensity is determined. Portions of 1, 5, 20, 25 and 30 microliters of the 1% solution are added to 8 oz. cups of IMH. The threshold flavor is evident to two expert tasters at 30ppm (10 microliters of 1% solution) with a woody flavor evident at 75ppm.
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A new alcohol, 8-methyl-non-2ynol and its derivatives has been discovered having a woody taste and flavor, and useful for enhancement of foodstuffs. The enhancement is achieved by the addition of a small but effective amount of said compounds to the food.
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BACKGROUND
[0001] 1. Technical Field
[0002] The present invention concerns a working platform assembly for use in the interior of a tower-like building.
[0003] 2. Description of the Related Art
[0004] When erecting a tower-like building such as for example a pylon of a wind power installation it is necessary inter alia also to carry out operations in the interior of the tower-like building. For that purpose typically a working platform assembly is fixed to a crane and introduced from above into the interior of the tower-like building. That is only possible however as long as the upper end of the tower-like building is open. As soon as the tower-like building is closed off upwardly it is no longer possible to use a working platform assembly on a crane. As the pylon of a wind power installation can attain for example a height of 100 meters operations in the interior of the pylon are not readily possible.
[0005] At this juncture as state of the art attention is directed generally to the following publications: DE 366 A; AT 203 033 and U.S. Pat. No 1,652,403.
BRIEF SUMMARY
[0006] Therefore the object of the present invention is to provide a working platform assembly which can be used in the interior of a tower-like building.
[0007] That object is attained by a working platform assembly as set forth in claim 1 and by a system for the use of a working platform assembly as set forth in claim 8 .
[0008] Thus there is provided a working platform assembly which can be used in the interior of a tower-like building such as for example a pylon of a wind power installation. The working platform assembly has a scissor lattice-like carrier structure. A working platform is arranged on that carrier structure.
[0009] Therefore there is provided a working platform assembly which can be adapted to different cross-sections. That is of significance in particular in relation to tower-like buildings whose cross-sections narrow upwardly so that the available area for a working platform assembly varies accordingly.
[0010] A scissor lattice-like support arrangement is provided as the carrier structure for a working platform assembly, which support arrangement climbs upwardly in the interior of a tower or pylon with the building progress and has a working platform assembly. Such a working platform assembly or internal platform assembly can advantageously be used in relation to towers or pylons which are made from pre-cast concrete parts.
[0011] The pre-cast concrete parts used for erecting a tower or pylon have at their inner periphery holders on which the inner platform assembly or parts thereof can be suspended. Preferably those holders are disposed at predetermined heights and spacings. Holders can either be mounted at the outset in the pre-cast concrete parts or they can be subsequently fitted therein. The holders which are arranged in a distributed configuration permit the working platform assembly to behave in a similar fashion to a mountain climber who drives hooks into a mountain face above his position and then continues to climb up to those hooks.
[0012] Subsequent fitment of those hooks is basically possible but is time-consuming. Thus the holders are preferably fitted at the start so that a working platform assembly can quickly climb up or down on those holders.
[0013] It will be noted however that subsequent installation may be appropriate if the alternative is temporary dismantling of the wind power installation pod as that requires considerably more effort.
[0014] In a preferred embodiment of the invention arranged around the central carrier element is an actuating element which acts on the lower scissor lattice bars which bear against the central carrier element. The lower scissor lattice bars can be subjected to a tensile force by the actuating element. That results in retraction of the scissor lattice and thus a reduction in the size of the working platform assembly so that it can be moved into a part of the tower which is of smaller cross-section. In contrast, acting on the scissor lattice bars with a pressure force results in extension of the scissor lattice structure and thus an increase in the size of the working platform assembly. If the working platform assembly already extends through the entire tower cross-section and bears against the wall of the tower the pressing force exerted on the scissor lattice bars can provide for adjusting the contact pressure with which the peripheral edge of the working platform assembly bears against the tower wall.
[0015] Further configurations of the invention are set forth in the appendant claims.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0016] The embodiments by way of example of the present invention are described in greater detail hereinafter with reference to the accompanying drawings in which:
[0017] FIGS. 1 to 4 each show a cross-section through a tower-like building in the erection of the building in accordance with the first embodiment,
[0018] FIG. 5 shows a sectional view of a tower-like building with a working platform assembly disposed therein,
[0019] FIG. 6 shows a cross-section through a tower-like building with a corresponding working platform assembly,
[0020] FIG. 7 shows a further cross-section of a tower-like building with a working platform assembly in accordance with the first embodiment, and
[0021] FIG. 8 shows a simplified view of an individual plate of the working platform assembly.
DETAILED DESCRIPTION
[0022] FIG. 1 shows a cross-section through a tower-like building 100 with a working platform assembly in accordance with the first embodiment. The building 100 which is in the course of construction, preferably a pylon of a wind power installation, has two pre-cast concrete parts 10 , 11 which were produced at the outset and which are arranged one upon the other. The working platform assembly 50 is lowered into the interior of the tower-like building by means of a crane cable 20 . In this example, the working platform assembly 50 substantially comprises a carrier structure which has scissor lattice-like carrier arms 5 , and a working platform 7 . A cable 2 may extend from a Tirak winch 1 for power input from the ground region. Tirak is a brand of winches well known in the art for lifting objects and other functions.
[0023] FIG. 2 shows a cross-section through a tower-like building with a working platform assembly in accordance with the first embodiment. While FIG. 1 shows a situation in which the working platform assembly is introduced into the interior of the tower-like building, FIG. 2 shows the situation in which the working platform assembly has been extended and extends completely across the tower cross-section. That is substantially achieved by the scissor lattice-like carrier arms 5 being extended until they are in contact with the inside wall of the tower-like building. A plurality of Tirak winches 1 are provided in the lower region of the working platform assembly. They are preferably each mounted to an outer end of each scissor lattice arm. People and material and tooling can be disposed on the platform 7 which preferably extends over the entire cross-section of the interior of the tower-like building. In that respect the platform 7 takes over the function of a working platform assembly and the people can there perform working steps in order to erect the tower-like building.
[0024] FIG. 3 shows a further cross-section through the tower-like building with a working platform assembly in accordance with the first embodiment. While only two pre-cast concrete parts 10 and 11 are shown in a condition of already being fitted in position in each of FIGS. 1 and 2 , FIG. 3 shows the situation in which a further pre-cast concrete part 12 is being mounted on the two pre-cast concrete parts 10 and 11 which have already been installed. Additional sections will be added as desired to build the pylon tower. In order on the one hand to secure the working platform assembly and on the other hand to permit it to climb in the interior of the tower, provided in the inside wall of the pre-cast concrete parts are holders 3 on which cables (not shown) are suspended. Those cables pass through the Tirak winches so that the platform assembly according to the invention can move in a vertical direction along the cables within the tower by suitable actuation of the Tirak winches.
[0025] A power supply for the working platform assembly and its Tirak winches can be provided for example by a cable 2 from below.
[0026] FIG. 4 shows a cross-section of a tower-like building with a working platform assembly in accordance with the first embodiment. Here, three pre-cast concrete parts 10 , 11 and 12 have now been assembled and the working platform assembly 50 has to be moved upwardly in order to permit operations to be carried out in the upper pre-cast concrete part 10 and/or fitment of the subsequent pre-cast concrete part. For that purpose one of the workers can climb by means of a ladder 15 to the holder 3 on the inside wall of the third pre-cast concrete part 12 in order to appropriately fix a cable of the Tirak winch 1 there. As an alternative to the ladder 15 it is also possible to use a telescopic bar. Preferably the number of holders 3 at the inside wall of the tower-like building should be at least equal to the number of Tirak winches so that the cables of the Tirak winches can be suitably fixed thereto. For that purpose, the brake on a respective winch is released so that the cable can be pulled upwardly. After the cable has been attached to the upper holder the cable is fixed in the winch again so that the platform assembly is also again carried by that cable. Thereupon the next winch is released and attached to the corresponding upper holder 3 , and so forth.
[0027] During those preparatory operations for displacing the working platform assembly within the tower it is repeatedly not held for a short time by a respective winch or the associated cable. The load of the working platform assembly must then be respectively carried by the other holders and cables.
[0028] FIG. 5 shows a cross-section through a tower-like building with a working platform assembly in accordance with the first embodiment. The scissor lattice-like carrier arms 5 of the working platform assembly are to be seen here. In addition the working platform assembly has rollers 16 ( 6 rollers are shown in this example but fewer or less can be used) externally on the working platform assembly. When the working platform assembly is extended the rollers then come into contact with the inside wall of the tower-like building so that the working platform assembly 50 can be more easily moved upwardly or downwardly and damage to the inside wall of the tower and/or the working platform assembly during the movement is avoided.
[0029] The platform includes a predetermined number of plates 17 , which is greater by 1 than the number of carrier arms. All plates 17 are of a circular round configuration in the present embodiment. One of those plates includes a central rod (see reference 60 in FIG. 6 ) in order to close the central part of the platform.
[0030] The other plates 17 are each arranged on a respective carrier arm and fixed to the outer end of the carrier arm. Those plates are further provided with an opening slot 19 . That opening 19 extends outwardly in a straight line in a radial direction from the center of the plate. In that respect the opening is of a width which is slightly greater than the diameter of the central rod. In situ each of those plates is so oriented that its opening faces towards the central rod 60 . As the arms 5 expand, the plates 17 spread apart, providing a larger platform 7 .
[0031] FIG. 6 shows a detailed sectional view through the working platform assembly shown in FIGS. 1 to 4 . In this case the scissor lattice-like carrier arms 5 are extended on the right-hand side. In that way a larger internal cross-section of the tower-like building can be covered by the working platform assembly.
[0032] FIG. 7 shows a further detailed cross-section of the tower-like building with the working platform assembly in accordance with the first embodiment. This FIG. 7 shows a situation in which the working platform assembly is disposed within a pre-cast concrete part 12 in the upper region of the tower-like building. In this case, the cross-section of that pre-cast concrete part is smaller than the cross-section of the pre-cast concrete part 10 shown in FIG. 6 . Accordingly the scissor lattice-like carrier arms 5 of the working platform assembly are adapted to the cross-section which decreases in size when the working platform assembly is displaced upwardly, by the arms being retracted.
[0033] Accordingly there can be provided an internal platform assembly or working platform assembly which can itself climb up or down in the tower. For example in the case of a pylon of a wind power installation it is no longer necessary to go up or down from the pod in a basket with a winch. Rather there is now provided an internal platform assembly which can extend completely across the pylon and which can easily climb up where precisely working operations are to be executed. Furthermore by virtue of the configuration of the scissor lattice-like carrier arms 5 it can adapt to different pylon cross-sections.
[0034] As soon as the working platform assembly is no longer required it can be retracted by the scissor lattice-like carrier arms being contracted. Thereafter the working platform assembly can be removed again for example through a door in the pylon of a wind power installation. Preferably the working platform assembly has a central rod 60 and scissor lattice/carrier arms 5 pivotably mounted thereto. Arranged on the carrier arms 5 are plates 17 which then form the working platform 7 . The so-called through-pass winches or Tirak winches are provided beneath the carrier arms. With Tirak or through-pass winches of that kind, the working platform assembly can itself climb up or down on cables extending through the winches. The cables of the Tirak winches 1 are preferably fixed to holders 3 at the inside of the tower-like building so that the Tirak winches can run up or down on the cables. Preferably a plurality of Tirak winches are provided at the periphery of the working platform assembly. For moving up or down the cables of the Tirak winches have to be successively released from the holders and fitted to the next higher or next lower holder, depending on whether the working platform assembly is to be moved up or down. Preferably there are at least five Tirak winches at the periphery of the working platform assembly so that there are also at least five cables with the corresponding holders 3 .
[0035] The plates 17 of the working platform are preferably of such a configuration that they overlap each other so that the working platform 7 can adapt to the different cross-sections within a tower-like building.
[0036] That adaptation operation takes place as follows. As the plates 17 of the working platform 7 overlap and do not lie in front of each other in butting relationship, they can move relative to each other. That movement of a plate 7 inevitably occurs upon actuation of the scissor lattice. When the scissor lattice is retracted the plate which is fixed thereto moves towards the central rod and vice-versa.
[0037] As each of the plates 17 in fixed to a carrier arm 5 has an opening which is directed towards the central rod and is somewhat wider than same retraction of a carrier arm with the concomitant movement of the corresponding plate 7 does not result in the plate 7 colliding with the central rod. Rather the opening moves towards the central rod and receives it. The length of the opening is a measurement of the extent to which the platform can be pushed together or the scissor lattice-like carrier arm can be retracted.
[0038] A simplified representation of a plate 17 is shown in FIG. 8 .
[0039] The rollers 6 at the periphery of the working platform assembly 50 are provided so that the working platform assembly rolls against the inside of the tower wall and does not scrape along it there.
[0040] The working platform assembly which is adjustable in its cross-section can provide a working platform which is adapted to the cross-section of a tower-like building which narrows upwardly.
[0041] The above-described working platform assembly is found to be particularly advantageous when a pod of a wind power installation is already arranged on the pylon of the wind power installation and there is thus no longer any possible way of gaining access to the interior of the pylon of the wind power installation by means of a crane from above. In such a situation the working platform assembly which can be collapsed or which can be dismantled can be introduced through the door in the lower region of the pylon and appropriately set up so that it can then move up and down along the pylon by means of the holders 3 which are disposed in the pylon segments.
[0042] As the scissor expands, the plate 17 that is fixed to the respective arm 5 also moves from the center, providing an enlargement of the platform 10 . As the arms are pushed together, the slots 19 go over central rod 60 , making the platform smaller.
[0043] The various embodiments described above can be combined to provide further embodiments. All of the U.S. patents, U.S. patent application publications, U.S. patent applications, foreign patents, foreign patent applications and non-patent publications referred to in this specification and/or listed in the Application Data Sheet, are incorporated herein by reference, in their entirety. Aspects of the embodiments can be modified, if necessary to employ concepts of the various patents, applications and publications to provide yet further embodiments.
[0044] These and other changes can be made to the embodiments in light of the above-detailed description. In general, in the following claims, the terms used should not be construed to limit the claims to the specific embodiments disclosed in the specification and the claims, but should be construed to include all possible embodiments along with the full scope of equivalents to which such claims are entitled. Accordingly, the claims are not limited by the disclosure.
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The invention concerns a working platform assembly for use in the interior of a tower-like building. The object of the present invention is to provide a working platform assembly which can be used in the interior of a tower-like building even if the tower is closed at the top by an upper structure thereon. According to the invention that object is attained by a scissor lattice-like carrier structure and a working platform arranged on the carrier structure. In that respect the invention is based on the that the working platform assembly according to the invention can be adapted to different inside diameters of the tower-like building by virtue of the scissor lattice-like carrier structure and can thus extend completely across the tower cross-section. That makes it possible to work on the platform assembly. The working platform assembly can be released from the tower wall by the scissor lattice-like carrier structure and fixed again in another region of the building of a different cross-section.
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CROSS REFERENCE TO RELATED APPLICATIONS
This Application claim priority under 35 U.S.C. §119 of Italian application number TO2001A 000445, filed May 11, 2001 in Italy.
BACKGROUND OF INVENTION
The present invention relates to a vane for a stator of a variable-geometry turbine, in particular of an axial turbine for aeronautical engines.
As is known, an axial turbine for an aeronautical engine comprises at least one stator and one rotor arranged in succession to each other and comprising respective arrays of vanes delimiting between them associated nozzles through which a flow of gas can pass.
In aeronautical engines, it has been found necessary to use axial turbines having relatively high efficiency in all operating conditions and, therefore, over a relatively wide range of values for the rate of flow of the gases that pass through the turbine itself.
This requirement could be met by producing variable-geometry turbines, i.e. turbines in which it is possible to vary the transverse area of the nozzles of at least one stator, in particular by adjusting the angular position of the stator vanes about respective axes incident to the axis of the turbine.
In use, however, the operating temperatures of the turbine are extremely high and involve considerable thermal expansion of the vanes and other components, so that jamming or outright seizure could occur between the movable vanes and the fixed parts of the stator, consequently compromising the functionality of the turbine.
SUMMARY OF INVENTION
The purpose of this invention is to produce a vane for a stator of a variable-geometry turbine, in particular for aeronautical engines, which allows the problems set out above to be solved simply and economically.
According to the present invention, a vane is produced for a stator of a variable-geometry turbine, in particular for aeronautical engines; the vane comprising an airfoil profile and means for coupling said airfoil profile to a support structure of said stator; characterised in that said coupling means comprise hinge means carried by said airfoil profile to allow rotation of the airfoil profile itself with respect to said support structure about an axis of adjustment, and in that it comprises means for cooling said hinge means.
The present invention also concerns a stator of a variable-geometry turbine, in particular for aeronautical engines.
According to the present invention, a stator of a variable-geometry turbine is produced, in particular for aeronautical engines; the stator comprising a support structure and a plurality of vane members delimiting between them a plurality of passages for a flow of gas; each vane comprising an airfoil profile and means for coupling said airfoil profile to said support structure; characterised in that said coupling means comprise hinge means carried by said airfoil profile to allow the rotation of the airfoil profile with respect to said support structure about an axis of adjustment, and in that it comprises means for cooling said hinge means.
BRIEF DESCRIPTION OF DRAWINGS
The invention will now be described with reference to the attached drawings, which illustrate a non-limiting embodiment of the invention, in which:
FIG. 1 is a schematic radial section of a preferred embodiment of the vane for a stator of a variable-geometry turbine, in particular for aeronautical engines, produced according to the present invention;
FIG. 2 illustrates in radial section and at a larger scale the vane in FIG. 1; and
FIG. 3 is a perspective view, with parts in section, of the vane in FIGS. 1 and 2 .
DETAILED DESCRIPTION
In FIG. 1, the number 1 indicates a variable-geometry axial turbine (shown schematically and in part), which constitutes part of an aeronautical engine, not shown.
The turbine 1 is axially symmetrical with respect to an axis 3 coinciding with the axis of the associated aeronautical engine and comprises an engine shaft 4 rotatable about the axis 3 and a case or casing 8 housing a succession of coaxial stages, only one of which is shown as 10 in FIG. 1 .
With reference to FIGS. 1 and 2, the stage 10 comprises a stator 11 and a rotor 12 keyed to the engine shaft 4 downstream from the stator 11 . The stator 11 in turn comprises a hub 16 (shown schematically and in part), which supports the engine shaft 4 in a known manner and is integrally connected to the casing 8 by means of a plurality of spokes 17 (FIG. 2) angularly equidistant from each other about the axis 3 .
As shown in FIG. 2, the stator 11 also comprises two annular platforms or walls 20 , 21 , which are arranged in an intermediate radial position between the hub 16 and the casing 8 and have the spokes 17 passing through them. The walls 20 , 21 are coupled, one with the casing 8 and the other with the hub 16 in substantially fixed datum positions by means of connecting devices 24 that allow the walls 20 , 21 themselves the possibility of axial and radial displacements of relatively limited amplitude with respect to the casing 8 and the hub 16 in order to compensate, in service, for the differences in thermal expansion between the various components.
The walls 20 , 21 have respective surfaces 27 , 28 facing each other and radially delimiting an annular duct 30 with a diameter increasing in the direction of travel of the gas flow that passes through the turbine 1 . The walls 20 , 21 carry an array of vanes 32 (only one of which is shown) angularly equidistant from each other about the axis 3 with the spokes 17 passing through them and comprising respective airfoil profiles 33 , which are housed in the duct 30 and between them circumferentially delimit a plurality of nozzles.
With reference to FIGS. 2 and 3, each vane 32 also comprises a pair of circular hinging flanges 36 , 37 , integral with the associated profile 33 , arranged at opposite ends of the profile 33 itself and coaxial with each other along an axis 40 , which is incident to the axis 3 and forms an angle other than 90° with the axis 3 .
The flanges 36 , 37 of each vane 32 engage rotatably in respective circular seatings 41 , 42 made in the walls 20 and 21 respectively to allow the associated profile 33 to rotate about the axis 40 .
With reference to FIG. 2, the flanges 36 , 37 of each vane 32 terminate in respective coaxial cylindrical sections 48 , 49 , of which the section 48 is caused to rotate in use by an angular positioning unit 50 (shown in part) comprising in particular a motor-driven actuating and synchronising ring 51 designed to rotate the profiles 33 simultaneously about the respective axes 40 through the same angle, keeping the profiles 33 themselves in the same orientation to each other with respect to the surfaces 27 , 28 . In particular, the maximum angular deflection of each vane 32 about the associated axis 40 is approximately 6°, while the zones of the surfaces 27 and 28 to which the profiles 33 are coupled slidably have a shape complementary to associated ideal surfaces generated by rotation of the profiles 33 .
The flanges 36 , 37 of each vane 32 are defined by respective circular plate portions, project from the associated profile 33 radially with respect to the axis 40 and are facing each other in the duct 30 .
The flange 37 is delimited by a cylindrical surface 59 directly and slidably coupled with the wall 21 in the seating 42 and by a flat surface 60 connecting the surface 59 to the section 49 , which is coupled to the wall 21 via an interposed spacer bush 68 constituting a friction bearing.
On the other hand, the flange 36 is delimited by a cylindrical surface 61 directly and slidably coupled with the wall 20 in the seating 41 and by a flat surface 62 , which connects the surface 61 to the section 48 , and against which is arranged an axially abutting radial lever 72 connecting the vane 32 to the ring 51 . In particular, the lever 72 is attached to the section 48 and is coupled with the wall 20 via an interposed spacer bush 73 constituting a friction bearing.
With reference to FIGS. 2 and 3, each vane 32 is cooled in use by a flow of air under pressure, which is conveyed into the case 8 in a known manner, not shown, and flows through a passage 81 made in the vane 32 itself and comprising an inlet 82 defined by the flange 36 , an outlet 84 defined by the flange 37 and an intermediate chamber 85 made in the profile 33 . The chamber 85 , in particular, communicates with the duct 30 via a plurality of holes (not shown) made in a tail portion of the profile 33 to cool the trailing edge of the profile 33 itself which, in use, is subject to severe thermal stresses.
The flow of cooling air removes heat from the flanges 36 , 37 by passing through the inlet 82 and the outlet 84 and also by means of channelling 86 inside the flanges 36 , 37 themselves. This channelling 86 comprises, for each flange 36 , 37 at least one associated pair of through-holes 87 (FIG. 2) made in positions diametrically opposite to each other and in a substantially radial direction, and an associated continuous circumferential groove 89 , which is made along the surface 59 , 61 close to the circular edge or corner of separation from the surface 60 , 62 and communicates with the chamber 85 via the holes 87 .
In use, the flow of cooling air is sent at a pressure of about 20 bar into the passage 81 , flows through the holes 87 and removes heat from the flanges 36 , 37 to limit the thermal expansion of the flanges 36 , 37 themselves.
The air sent into the grooves 89 , at the same time, forms a film or cushion of air that performs not only a load-bearing function during rotation of the vanes, limiting the friction forces between flanges 36 , 37 and walls 20 , 21 , but above all a sealing function preventing the flow of gas from flowing out of the duct 30 through the clearances formed between the vanes 32 and the walls 20 , 21 in the seatings 41 , 42 .
In other words, in the grooves 89 the cushion of air constitutes a sort of virtual sealing ring that avoids the use of sealing gaskets between the vanes 32 and the walls 20 , 21 .
From the above, it is evident that the vanes 32 enable the geometry of the nozzles of the stator 11 to be adjusted in use, the vanes being hinged to the walls 20 , 21 , and at the same time avoid jamming and seizure against the walls 20 , 21 during adjustment, being cooled at the flanges 36 , 37 .
In fact, the removal of heat by means of the flow of air that passes through the passage 81 and the channelling 86 makes it possible to limit the thermal expansion of the flanges 36 , 37 and thus to control the clearances between the flanges 36 , 37 themselves and the walls 20 , 21 in order to obtain correct and always precise angular positioning of the vanes 32 about the respective axes 40 .
Moreover, as already stated, the fact of causing air to flow along the surfaces 59 , 61 makes it possible to produce a cushion of air that limits the friction between the flanges 36 , 37 and the walls 20 , 21 and therefore contributes significantly to obtaining precise angular positioning of the vanes 32 and thus correct operation of the turbine 1 , achieving high levels of efficiency in all operating conditions of the associated aeronautical engine.
Finally, it is evident from the above that modifications and variations can be made to the vane 32 described and illustrated, without extending it beyond the scope of protection of the present invention.
In particular, the vane 32 could have hinge portions different from those described and illustrated and/or cooling fluids or channels different from those indicated could be provided. For example, the cushions of air that are formed in use between the flanges 36 , 37 and the walls 20 , 21 could be obtained by producing seatings in the walls 20 , 21 instead of in the vanes 32 , or a simple chamfer along the corners between the surfaces 59 , 61 and the surfaces 60 , 62 . Moreover, a labyrinth seating could be provided instead of a simple groove 89 on the flanges 36 , 37 .
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A vane for a stator of a variable-geometry turbine, in particular for aeronautical engines, has an airfoil profile and a pair of hinge portions, which are carried by the airfoil profile and enable the airfoil profile to be coupled to a support structure of the stator so as to be rotatable about an axis of adjustment; the vane also has internal channels that allow a flow of air to pass through in order to cool the hinge portions.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention is generally related to a lift boat or jack-up rig and more particularly to the mechanism for raising and lowering the legs of a lift boat or jack-up rig.
[0003] 2. General Background
[0004] In offshore work related to the search for and production of oil and gas, a variety of vessel types are used. One type is a lift boat. A lift boat is a vessel that can elevate itself out of the water so as to provide a stable platform at the appropriate elevation to perform a number of marine construction tasks. Lift boats are equipped with retractable legs that each has a footing at the bottom. The footings contact the bottom and are of sufficient size to support the vessel on the seabed. The number of legs can vary from three to as many as six. One or more cranes are fixed to the deck of the vessel and are used to lift equipment onto or off of oil drilling or production platforms. A larger version of the lift boat called a jack-up rig typically is outfitted with drilling equipment. From this point on all mention of lift boats shall also be understood as including jack-up rigs.
[0005] At least one gear rack is typically incorporated into each leg of a lift boat. The legs of a lift boat are either constructed as a lattice type or as a tubular type. One or more pinion assemblies operate along each gear rack. A pinion assembly typically consists of a pinion, gear box, braking mechanism and either an electric or hydraulic motor. The pinion assemblies are either rigidly fixed to the vessel or can be of the floating type. As the pinions of the lift boat rotate, the lift boat is either raised out of the water or lowered toward the surface of the water depending upon the direction of pinion rotation.
[0006] The legs can be somewhat self-centering if multiple gear racks are used on the legs and if the gear racks are arranged properly. Even if the racks are ideally numbered and positioned some side loading of the legs will occur due to sea, wind, and vessel loading conditions. The current generation of lift boats employs a linear metal bearing guide to restrict leg movement. This guide system consists of metal bearing strips attached to the vessel or to the jacking apparatus. The guides may ride along the gear rack, the leg cords, or attachments to either the leg or gear rack. Smaller lift boats have leg towers constructed from tubular members and have tubular legs with outside diameters slightly smaller than the inside diameters of the leg towers. The leg tower is the sole guide. The shortcomings of these types of guide apparatus are that friction between the leg and guides increases the jacking force required to operate the lift boat and much of the lubricant used on the guides is dropped into the sea.
SUMMARY OF THE INVENTION
[0007] The present invention addresses the above needs in a straightforward manner. What is provided is an apparatus for efficiently guiding the legs of a lift boat. Roller assemblies are used to guide the legs. The rollers may be placed at any location or in any number either vertically or around the leg to adequately center the leg. The roller can either have a metal surface that rolls along the leg or be coated with a resilient material. The base of the roller can either be rigidly mounted to the vessel or incorporate resilient material between the roller and the vessel. A means of adjusting the clearance between the leg and roller may be incorporated in the roller assembly.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] For a further understanding of the nature and objects of the present invention reference should be made to the following description, taken in conjunction with the accompanying drawings in which like parts are given like reference numerals, and wherein:
[0009] [0009]FIG. 1 is an isometric view of a lift boat.
[0010] [0010]FIG. 2 is a detail view of a jacking and guide apparatus.
[0011] [0011]FIG. 3 is an isometric view of the guide roller assembly.
[0012] [0012]FIG. 4 is an exploded view of the guide roller assembly.
[0013] [0013]FIG. 5 illustrates an alternate embodiment of the invention.
[0014] [0014]FIG. 6 is a detail view of the alternate embodiment of FIG. 5.
[0015] [0015]FIG. 7 is a detail view of another alternate embodiment of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0016] Referring to FIG. 1, it is seen that a typical lift boat is generally indicated by the numeral 10 . For ease of illustration the lift boat's deckhouse, cranes and all deck equipment have been omitted. The lift boat is generally comprised of a hull 12 and a plurality of legs 14 . The hull 12 is a buoyant hull that has sufficient buoyancy to support the hull, legs, and any equipment placed on the hull. As seen in FIG. 1, the lift boat is elevated above the water's surface 30 . As seen in FIG. 2 each leg 14 is received through a leg well 34 provided near each corner of the hull 12 . The outer diameter of each leg 14 is less than the diameter of the leg well 34 so as to be movable through the hull 12 . Although only a tubular column 20 is shown, it should be understood that the legs 14 may be formed from either a tubular or lattice column. Each leg 14 is provided with a rack 22 and a footing 24 . The legs 14 may have singular or multiple racks 22 . The leg 14 is raised and lowered through the hull 12 by a pinion tower 18 . Each rack 22 may have singular or multiple pinions 32 . Multiple pinion towers 18 may be separately attached to the hull 12 or may be integrated into a unit attached to the hull 12 . The footings 24 are of sufficient size to provide resistance to the seabed 28 to allow the pinion tower 18 to elevate the hull 12 above the surface of the water.
[0017] Referring to FIG. 2- 4 , it is seen that the invention is generally indicated by the numeral 26 . Guide roller apparatus 26 is generally comprised of a support box 36 , a pivot arm 38 and a roller 40 .
[0018] The support box 36 is formed from two or more support box side plates 42 that are attached to a support box back plate 46 and a support box bottom plate 44 . A support box pin 48 connects the pivot arm 38 to the support box 36 . A keeper 50 prevents the support box pin 48 from sliding out of the support box 36 . The keeper 50 is attached to the support box 36 by any suitable means such as by welding, mechanical fastener, or by the use of an adhesive.
[0019] The pivot arm 38 is of suitable shape to transfer forces from the leg 14 to the hull 12 . The pivot arm 38 is formed from two or more pivot arm side plates 52 that are attached to a pivot arm back plate 68 . A pivot arm pin 56 connects the roller 40 to the pivot arm side plate 52 . A keeper 51 prevents the pivot arm pin 56 from sliding out of the pivot arm side plates 52 .
[0020] The roller 40 is of suitable shape to transfer forces from the leg 14 to the hull 12 . A bushing 58 , an inner core 60 , and an outer core 62 are assembled together to make up the roller 40 . The bushing 58 is of suitable shape and material to allow it, the inner core 60 , and the outer core 62 to rotate around pin 56 . The bushing 58 may be constructed of non-lubricated or lubricated material. The bushing 58 is attached to the inner core 60 by interference fit, bonded, or keyed to prevent relative movement. The inner core is constructed of suitable rigid material such as steel and attached to the outer core 62 by interference fit or bonded to prevent relative movement. The outer core 62 is formed from a suitable resilient material such as neoprene.
[0021] One or more spacer plates 64 are of suitable shape and material to transfer forces from the leg 14 to the hull 12 . Resilient plate 66 is of suitable shape and material to transfer forces form the leg 14 to the hull 12 . Spacer plates 64 may be of varying thickness and number to adjust the nominal distance between the roller 40 and the leg 14 from a clearance to a compressed pre-load. In a pre-load condition the resilient outer roller 62 and the resilient plate 66 are deformed so that during normal operating conditions there is no clearance between roller 40 and leg 14 .
[0022] The guide roller apparatus 26 may be securely attached to either the hull 12 , pinion tower 18 or, as seen in FIG. 2, to a guide roller tower 16 . The guide roller apparatus 26 may be the sole means of guiding the leg 14 or may be used in conjunction with bearing strips or any other suitable guide apparatus. The guide roller apparatus 26 may be set to a desired clearance or pre-load to the leg column 20 , rack 22 , or any attachment to either. The roller apparatus 26 is of sufficient size, number and location to adequately restrict the leg 14 to movement with the hull 12 . The guide roller tower 16 may be attached directly to the hull 12 or incorporated into the hull 12 , pinion tower 18 or other parts of the lift boat 10 .
[0023] In operation, as the legs 14 are moved up or down through the hull 12 , the guide roller apparatus 26 on each leg 14 confines each leg 14 to a near perpendicular orientation relative to the deck of the hull 12 . The advantage this provides is that it prevents any out of alignment movement, which decreases the efficiency of the driving system and increases the possibility of damage.
[0024] An alternate embodiment of the invention is generally indicated by numeral 70 in FIG. 5 and 6 . Track guide apparatus 70 is generally comprised of track 92 , rail structure 90 , idlers 76 and rollers 86 . For ease of illustration, the hull and pinion tower are not shown.
[0025] A leg tower 74 is attached to the lift boat and is sized to allow movement of the leg 14 therethrough. The leg tower 74 is provided with an elongated opening 72 . Track guide apparatus 70 is attached to the leg tower 74 and contacts the leg 20 through the elongated opening 72 in the leg tower.
[0026] As best seen in FIG. 6, the track 92 is comprised of link plates 88 , link pins 78 , and track pads 84 traveling around idlers 76 . The force exerted upon the track 92 by the leg 20 is transferred to the rail structure 90 via the rollers 86 . The rollers may be of a similar design as shown in FIG. 4 or of any other design suitable to transfer the force. The rail structure generally indicated by numeral 90 is comprised of a rail 82 and rail flanges 80 . The rail flanges 80 are attached to the leg tower 74 .
[0027] [0027]FIG. 7 illustrates a second alternate embodiment of the invention. The alternate track guide apparatus is generally indicated by the numeral 102 . The link 94 and pins 96 are similar to the link and pin shown in FIG. 5 and 6 . Roller 98 contacts the rail 100 and the leg, not shown. Roller 98 may be incorporated with the pin 96 as one component. For clarity, the rail flanges that attach the rail to the tower are not shown.
[0028] Because many varying and differing embodiments may be made within the scope of the inventive concept herein taught and because many modifications may be made in the embodiment herein detailed in accordance with the descriptive requirement of the law, it is to be understood that the details herein re to be interpreted as illustrative and not in a limiting sense.
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An apparatus for efficiently guiding the legs of a lift boat. Roller assemblies are used to guide the legs. The rollers may be placed at any location or in any number either vertically or around the leg to adequately center the leg. The roller can either have a metal surface that rolls along the leg or be coated with a resilient material. The base of the roller can either be rigidly mounted to the vessel or incorporate resilient material between the roller and the vessel. A means of adjusting the clearance between the leg and roller may be incorporated in the roller assembly.
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This application claims priority to U.S. provisional Patent Application No. 61/245,972 filed Sep. 25, 2009, titled “Rate Shaping Triggered Discontinuous Transmission in Wireless Communications,” the disclosure of which is incorporated herein by reference in its entirety.
FIELD OF INVENTION
The present invention relates generally to wireless communication networks, and in particular to a system and method of controlling discontinuous transmission by rate shaping.
BACKGROUND
Wireless communication systems are a ubiquitous part of modern life in many areas. A number of different wireless communication protocols have been developed. For example, Long Term Evolution (LTE) is a set of enhancements to the Universal Mobile Telecommunications System (UMTS) that supports high data rates, low latency, low implementation and operating costs, and a seamless connection to legacy wireless communication networks.
As another example, High Speed Packet Access (HSPA) is an extension of wideband CDMA (WCDMA) protocols. HSPA transmits communication data on shared channels, in packets addressed to specific users. HSPA features short Transmission Time Interval (TTI), link adaptation, fast scheduling, fast retransmission and soft-combining, and advanced modulation, resulting in increased data rates, low latency, and increased system capacity.
A limitation common to all wireless communication systems is the limited battery life of mobile terminals, or user equipment (UE). One known method to preserve UE battery life, supported by numerous wireless communication protocols, is Discontinuous Reception (DRX). DRX reduces battery consumption in the UE by allowing the UE to stop monitoring a downlink control channel, such as the Physical Downlink Control Channel (PDCCH). That is, the UE can turn off its receiver during certain time periods. The time periods during which the receiver is turned off are configured by the network. DRX is configured separately—that is, by means of different parameters—for UEs in RRC_IDLE and RRC_CONNECTED mode.
FIG. 1 depicts the basics of DRX. Periodically, the UE has an “on duration,” during which time it monitors the system for traffic. Following the “on duration” is an opportunity for DRX—that is, a period during which the UE may be relieved from monitoring the system for traffic, thus reducing power consumption and conserving battery power. At the end of the DRX Cycle, the process repeats with another “on duration” and another opportunity for DRX.
The DRX Command MAC Control Element is specified in the 3GPP Technical Specification 36.321, “MAC Protocol specification,” the disclosure of which is incorporated herein by reference in its entirety. The DRX Command MAC Control Element can be used to force the UE into DRX sleep mode. If a DRX Command MAC control element is received, both the On Duration Timer and the DRX Inactivity Timer shall be stopped. Furthermore, upon reception of a DRX Command MAC Control Element the DRX Short Cycle Timer shall be started/restarted and the short DRX cycle should be run if configured. The MAC Subheader is depicted in FIG. 2 .
An inactivity timer specifies the number of consecutive downlink subframes during which the UE shall monitor the PDCCH after successfully decoding a PDCCH indicating an initial UL or DL user data transmission for this UE.
The DRX Short Cycle Timer parameter specifies the number of consecutive subframes the UE shall follow the short DRX cycle after the DRX Inactivity Timer has expired. FIG. 3 depicts these relationships. If the UE has decoded a PDCCH indicating new transmission during its “on duration,” the inactivity timer will keep the UE from sleeping after sending uplink (UL) data—that is, it will prevent the UE from stopping its monitoring of PDCCH. After the inactivity timer has expired the Short Cycle Timer is started. The Short Cycle Timer allows up to five Short Cycles, during which the UE may again monitor the PDCCH.
The process of delaying packets in a traffic stream to cause the traffic to conform to some defined profile is called rate shaping or traffic shaping. Rate shaping may be applied, for example, to smooth out traffic in time entering a network. In the enhanced NodeB (eNodeB) of LTE, rate shaping is applied to a number of bearers, effectively shaping on an aggregate bitrate.
A known rate shaping algorithm is the so-called token bucket algorithm, described in Annex B of the 3GPP Technical Standard 23.107, “Quality of Service (QoS) concept and architecture,” incorporated herein by reference in its entirety. The basis for this algorithm is an analogy to a bucket of fixed size, into which tokens, representing an allowed data volume, are injected at a constant rage. These tokens accumulate in the bucket, and the maximum allowed number of tokens is defined by the bucket size. The tokens are consumed by the data packets transmitted. Accordingly, if there are at least as many tokens in the bucket as the packet size, then the packet may be transmitted. Conversely, if the packet size is larger than the number of tokens currently in the bucket, the packet is delayed until sufficient tokens accumulate in the bucket. The parameters defining the token bucket are the token rate, r, and the bucket size, b. A token bucket counter (TBC) variable is used to hold the current number of tokens in the bucket. The token rate corresponds to the maximum or guaranteed bit rate and the bucket size corresponds to the bounded burst size. Data is conformant if the data sent in an arbitrary time period, T, does not exceed b+rT.
FIG. 4 depicts a visualization of the conventional token bucket algorithm applied to rate control over several bearers. At most b tokens can be stored in the bucket and the resulting rate, R, is on average the token rate, r.
FIG. 5 depicts the operation of the token bucket algorithm. Initially, the bucket is assumed full, with TBC=b. A first packet, of length l 1 , is conformant (sufficient tokens are in the bucket), and it is passed to the wireless network for transmission. The bucket fills at a constant rate over the next interval Δt=t 2 −t 1 , until a second packet, of length l 2 , arrives. The second packet is also conformant (it is smaller than the number of tokens in the bucket, or l 2 <TBC), and the packet is passed by the rate shaper. A third packet arrives, of length l 3 , when the bucket contains just enough tokens to pass it as well—completely or nearly depleting the bucket (TBC at or near 0). A fourth packet, of length l 4 , arrives at time t 4 , before the bucket has been sufficiently replenished with tokens. The fourth packet is delayed by the rate shaper until TBC>=l 4 , indicated in FIG. 5 as “Packet delay.”
SUMMARY
According to one or more embodiments described and claimed herein, a modified token bucket rate shaping algorithm creates known durations during which not traffic is passed; during these times, a UE may be safely forced in to DRX mode to conserve battery power. The modified token bucket algorithm allows for the “borrowing” of tokens, creating the possibility of a token debt, or a token bucket with a negative TBC value. In this modified token bucket algorithm, an incoming packet is passed along so long as the TBC is positive, even if the packet must “borrow” some tokens, driving the TBC negative. Subsequent incoming packets are stalled until the TBC reaches a positive value. The token bucket refills at a known rate; accordingly, the duration of traffic stalling is known. During this time of stalled traffic, the UE is forced into DRX mode, saving battery power by not monitoring DPCCH for traffic that has been halted. The DRX, or sleep, mode may be invoked in several ways.
One embodiment relates to a method of controlling DRX in UE based on rate shaping by a wireless communication network. Traffic transmitted by the network is rate shaped using a modified token bucket rate shaping algorithm comprising by maintaining a token bucket counter (TBC) representing the number of tokens in a bucket; decreasing the TBC by the size of each packet passed for transmission by the network; increasing the TBC at a constant token rate; if the TBC is positive, passing a data packet for transmission by the network; and if the TBC is negative, withholding a data packet from transmission by the network. If the TBC is negative, a UE is directed to enter a DRX mode in which the UE does not monitor a downlink control channel for downlink traffic.
Another embodiment relates to a wireless communication network. The network includes a rate shaper operative to limit data transmitted by the network using a modified token bucket rate shaping algorithm. The algorithm includes maintaining a token bucket counter (TBC) representing the number of tokens in a bucket; decreasing the TBC by the size of each packet passed for transmission by the network; increasing the TBC at a constant token rate; if the TBC is positive, passing a data packet for transmission by the network; and if the TBC is negative, withholding a data packet from transmission by the network. The network further includes a controller operative to direct a UE to enter a DRX mode in which the UE does not monitor a downlink control channel for downlink traffic if the TBC is negative.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a timing diagram demonstrating DRX operation.
FIG. 2 is a diagram of a MAC subheader.
FIG. 3 is a detailed timing diagram of DRX operation.
FIG. 4 is a functional block diagram of a conventional token bucket algorithm for a rate shaper.
FIG. 5 is a graph depicting the operation of a conventional token bucket algorithm in a rate shaper.
FIG. 6 is a graph depicting the operation of a modified token bucket algorithm with token debt, in a rate shaper.
FIG. 7 is graph depicting the delay in packet throughput when tokens are borrowed in a modified token bucket algorithm.
FIG. 8 depicts the relationship between the modified token bucket algorithm operation and DRX operation according to a first embodiment.
FIG. 9 depicts the relationship between the modified token bucket algorithm operation and DRX operation according to a second embodiment.
FIG. 10 is a timing diagram depicting DRX operation according to a third embodiment.
FIG. 11 is a timing diagram depicting DRX operation according to an embodiment that does not require alteration of wireless communication protocol standards.
FIG. 12 depicts the relationship between the modified token bucket algorithm operation and DRX operation when a UE has uplink transmissions.
FIG. 13 is a timing diagram depicting prior art DRX operation requiring the UE to monitor PDCCH for data.
FIG. 14 is a flow diagram depicting the DRX algorithm according to embodiments of the present invention.
DETAILED DESCRIPTION
In a modified token bucket algorithm that introduces token borrowing, a packet is allowed to create a token debt, resulting in a negative TBC. After creating such a token debt, the modified algorithm will not pass any further packets until the TBC has resumed a positive value. Thus, the borrowing will create a delay before the next transmission is allowed, during which a UE is directed to assume DRX mode. The lower bound on the TBC is −c so that the TBC is within the range [−c,b]. In some embodiments, the TBC may also be bounded by the available radio channel.
In an exemplary embodiment, the TBC is increased by r in each unit time up to the bucket size, b. In another embodiment, the TBC is increased by Δt·r where Δt is the time difference between the current time and the previous update of the TBC.
When the l th packet with length l i arrives, the modified algorithm checks if the TBC value is equal or greater than zero. If so, then traffic is conformant and TBC is decreased by l i (even if TBC <l i ). If the TBC is less than zero, the packet is delayed until the TBC is equal or greater than zero.
The operation of this modified token bucket algorithm is depicted in FIG. 6 . Four packets with lengths l 1 , l 2 , l 3 , and l 4 arrive, of which the first two are conformant and therefore processed immediately, as in the conventional token bucket algorithm. The third is conformant under the modified token bucket algorithm, but it makes the TBC go below zero. When the fourth packet arrives at t 4 , TBC <0, so the packet is delayed until the TBC is greater than zero, as indicated in FIG. 6 by the “Packet delay” duration.
In the modified token bucket algorithm, the maximum number of tokens, b, is determined by the parameter bucketTime [s] so that b=r·bucketTime. The parameter bucketTime corresponds to the time it is possible to save tokens to be consumed in a burst which does not cause any debt. In other words, a rate shaper employing the modified token bucket algorithm allows data bursts that comprise as much data as what may be sent in steady state with a constant rate, r, for the duration of
b
+
c
r
.
FIG. 7 depicts the delay imposed by the rate shaper due to a negative TBC in the modified token bucket algorithm. If the TBC becomes negative due to a large packet, then the UE cannot send or receive any data during a time period Δt. Since tokens are refilled at a token rate, r, the time is defined by the number of borrowed tokens divided by the token rate. During the time Δt that the modified token bucket algorithm denies scheduling of the UE, the UE wastes battery power monitoring PDCCH while waiting for new data.
According to embodiments of the present invention, a DRX, or sleep period is triggered for a UE when the rate shaping algorithm imposes periods of inactivity. As depicted in FIG. 7 , if the TBC becomes negative then the system cannot send, and the UE cannot receive, data during a time period Δt. Since tokens are refilled with a token rate, r, the time is defined by the number of borrowed tokens divided by the token rate. During this time period the UE will not be scheduled, and is therefore forced into DRX mode, so that it does not waste battery power monitoring the PDCCH. The time the UE should sleep is at most Δt.
In a first embodiment, as depicted in FIG. 8 , the UE is forced to sleep for Δt using a modified MAC Control Element. The modification includes adding a field for the DRX duration Δt=t 4 −t 3 . This could occur within an “on” duration. As shown, the UE is forced to sleep for part of the second “on” duration. This embodiment yields maximum conservation of UE battery power, but requires modification of the system standards to include the Δt field in the MAC Control Element.
In a second embodiment, as depicted in FIG. 9 , the UE is forced to sleep only until the next “on” duration (DRX long cycle) using the MAC Control Element. In this embodiment, the DRX rhythm is not disturbed. In this embodiment, note that the UE is active for the entire second “on” duration, but cannot receive data for the first part of it (until Δt expires and the TBC>=0).
In a third embodiment, as depicted in FIG. 10 , the UE is forced to sleep several DRX long cycles using a modified MAC Control Element. The modified MAC Control Element contains the number of DRX cycles to skip. Alternatively, as depicted in FIG. 11 , the UE sleep period can be triggered at each “on” duration with an unmodified MAC Control Element. In both cases, the UE is depicted transmitting uplink (UL) data immediately after receiving the downlink (DL) data that triggers the token bucket debt.
As depicted in FIG. 12 , if the UE has data to send in the UL direction, it will monitor PDCCH in order to send that data and sleep for the remainder of Δt. This will allow, for example, Transmission Control Program (TCP) acknowledgements (ACKs) to be sent before sleeping. In this case, the UE monitors the PDCCH for the duration indicated, to receive scheduling grants.
Assume a TCP flow is rate shaped to a particular rate, called the shaping rate. The shaping rate will on average be the token rate. However, since TCP probes for more bandwidth, some packets have to be stored in the eNodeB. At most, around one Pipe Capacity worth of data will reside in the buffer. The Pipe Capacity (PC) or the bandwidth delay product (BDP) is defined as the bandwidth times the round trip time (RTT) for the flow: PC=R·RTT.
For rate shaping, a parameter r is defined to be the rate at which the token bucket is refilled with tokens. On average, the flow will adapt to this rate, yielding the relation r=R (see FIG. 3 ). The time, Δt, in which the network is prohibited to send traffic to the UE is then
Δ t = PC r = R · RTT r = RTT ,
that is, the maximum time that the UE does not receive data is one RTT. Note also that the time is independent of the token rate and the current bitrate. The round trip time is on the order of tenths or even hundreds of milliseconds; for example, RTT can be within the range 40 ms to 400 ms.
The buffer size will be at most the minimum age threshold of the Active Queue Management algorithm in the eNodeB, regardless of the actual RTT. This minimum age threshold has the default value 200 ms. The RTT may be substituted for the minAgeThreshold, here denoted by t min , so Δt=t min . This is the maximum amount of data that can be sent. In practice, the rate is limited by the cell peakrate in each TTI. Accordingly,
Δ t = min ( t min , R · 10 - 3 r ) ,
where R is the peak rate and r is the token rate. The peak rate R is multiplied by 1 millisecond to give the maximum number of bits that can be transferred in one TTI.
T is defined as the duration that no data is sent, even if allowed. The following relationships apply:
0 ≤ T ≤ R · 10 - 3 r , 0 ≤ Δ t ≤ R · 10 - 3 r , and T + Δ t = R · 10 - 3 r .
The value of T will affect the potential duration of DRX mode since
Δ t = R · 10 - 3 r - T .
T has been found from simulations to be a few milliseconds.
The following example illustrates the battery power savings of embodiments of the present invention, in the case when Δt is 120 ms, i.e., three DRX long cycles t c . The “on” duration t on is 2 ms. The inactivity timer value t inactive is 40 ms. FIG. 13 depicts the prior art situation, wherein the UE is awake during three DRX cycles, 4t on +t inactive . The awake ratio is
4
t
on
+
t
inactive
3
t
c
.
In contrast, FIG. 10 depicts the situation when embodiments of the present invention are applied. In the DRX Short cycle, data is sent first in DL and then in UL, taking 2 ms in total. The DL rate shaping function triggers after sending the DL data and the UE sleep period is triggered. The UE however has UL data to send and does this before sleeping for the remainder of Δt. The inactivity timer is bypassed, resulting in lower battery power consumption. Note that the UE sleep period may be triggered either once or at every “on” duration start. In this case, the UE is awake during three DRX cycles, t on . The awake ratio is
t
on
3
t
c
.
By allowing the UE to go into the DRX short cycle, almost the same performance can be achieved without the need to alter system standards. FIG. 11 depicts an example using a DRX short cycle timer of 2 DRX short cycles. In this case, the UE is awake during three DRX cycles 3t on . The awake ratio is
3
t
on
3
t
c
.
The amount of battery power saved is thus dependant on the DRX settings and Δt. In this case when Δt is 120 ms, t c and t inactive are 40 ms, and t on is 2 ms, the savings is (3t on +t inactive ) on average per three DRX cycles. That is,
4
t
on
+
t
inactive
-
t
on
4
t
on
+
t
inactive
≈
0.96
In embodiments that do not require any changes to the system standards,
4
t
on
+
t
inactive
-
3
t
on
4
t
on
+
t
inactive
≈
0.88
FIG. 14 depicts a method 100 of controlling DRX in a UE based on a modified token bucket rate shaping algorithm for the downlink. Initially, the Token Bucket Counter (TBC) is set to b (block 102 ) representing the maximum number of tokens it can hold. The TBC is incremented at a constant token rate r (block 104 ). The increase in TBC is depicted as a discrete block 104 ; however, those of skill in the art will recognize that the TBC is incremented at a constant rate, regardless of the flow of control through the flow diagram of FIG. 14 . In one embodiment, for example, the TBC is incremented each TTI. The rate shaper receives one or more data packets of user traffic (block 106 ). If the TBC is greater than or equal to zero (block 108 ), the packets are deemed conformant and passed on for transmission by the network (block 114 ), and the TBC is decremented by the packet size (block 116 ). In this case, DRX is disabled at the UE (block 112 ), if necessary. As noted above, this may create a negative value in the TBC, representing “borrowed” tokens. If one or more traffic packets are received (block 106 ) and the TBC is negative (block 108 ), the packets are withheld from transmission. Since no user traffic is to be transmitted on the downlink, a DRX command is sent to the UE (block 110 ), such as in a MAC Control Element, directing the UE to a sleep mode to conserve battery power.
Those of skill in the art will readily recognize that a rate shaper implementing the method 100 may be implemented in dedicated hardware, programmable logic with appropriate firmware, software executing on a controller or processor (e.g., a Digital Signal Processor, or DSP), or any combination thereof. Such firmware or software may be stored on non-transient computer-readable media, such as solid-state memory (e.g., Flash RAM, DRAM, ROM, or the like), magnetic or optical media, or the like. The firmware or software may be accessed by a controller or processor directly, via a controller such as a memory controller or disc drive controller, or across a wired or wireless network from remote computer readable media.
In a first embodiment described herein, the inactivity timer is bypassed, allowing the UE to save battery power. This embodiment requires changes to the system operating standards, but offers the best performance.
A second embodiment described herein does not disturb the DRX cycle, but does not save as much battery power as the first embodiment. The inactivity timer is bypassed completely. This embodiment does not require any changes to the system operating standards.
A third embodiment described herein allows the UE to sleep through several “on” durations, but requires changes to the system operating standards. Alternatively, the UE can be triggered once for each “on” duration—a solution not requiring any changes to the system operating standards. This embodiment yields a good performance increase without too much effort.
By utilizing DRX functionality, it is possible to extend the UE's battery life time by periodically switching off the UE transceiver in an organized manner. The modified DRX functionality disclosed herein makes use of information in the rate shaping mechanism to predict periods of inactivity, in order to save even more battery power. Although explained herein in detail with reference an embodiments implementing a modified token bucket algorithm with token borrowing, the present invention is not limited to such an embodiment. In general, UE battery life may be extended by activating DRX whenever a rate shaping mechanism is able to identify, or predict, a duration of non-transmission of data by the network.
As used herein, the following terms have the following defined meanings:
Rate enforcement: Rate enforcement is the umbrella term for rate shaping and rate policing.
Rate policing: The process of discarding packets from a traffic stream in accordance with a traffic profile is called rate policing or traffic policing. Reasons to apply rate policing can be to protect the network from flooding attacks, enable tiered subscriptions and discourage cheating, e.g., users upgrade the VoIP codec rate beyond that which has been authorized by the network.
Rate shaping: The process of delaying packets in a traffic stream to cause it to conform to some defined traffic profile is called rate shaping or traffic shaping. Reasons to apply rate shaping can be to smooth out traffic in time entering a network. The reasons to apply rate policing are valid also here. Rate shaping can be realized as an improvement to the scheduler.
Shaping rate: The rate resulting from the use of a rate shaper with a certain token rate. The shaping rate should on average be the token rate.
Traffic policing: See rate policing.
Traffic shaping: See rate shaping.
Token: Something serving as an expression of something else. Here a token is virtual sign corresponding to the smallest information unit size. Tokens arrive into the bucket at the token rate, r.
Token rate: The rate at which tokens are injected into the system.
The present invention may, of course, be carried out in other ways than those specifically set forth herein without departing from essential characteristics of the invention. The present embodiments are to be considered in all respects as illustrative and not restrictive, and all changes coming within the meaning and equivalency range of the appended claims are intended to be embraced therein.
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A modified token bucket algorithm in a rate shaper in a wireless communication network allows for the “borrowing” of tokens, creating the possibility of a token debt, or a token bucket with a negative Token Bucket Counter (TBC) value. In this modified token bucket algorithm, an incoming packet is passed along so long as the TBC is positive, even if the packet must “borrow” some tokens, driving the TBC negative. Subsequent incoming packets are stalled until the TBC reaches a positive value. The token bucket refills at a known rate; accordingly, the duration of traffic stalling, when the TBC is negative, is known. During this time, the UE is forced into DRX mode, saving battery power by not monitoring DPCCH for traffic that has been halted. The DRX, or sleep, mode may be invoked in several ways.
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